Color photographic light-sensitive material for printing use

ABSTRACT

A color photographic light-sensitive material for printing use comprising a reflection type support bearing thereon a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer; wherein a silver halide emulsion contained in said green-sensitive silver halide emulsion layer is a monodispersed silver halide emulsion and a coupler combined with said monodispersed silver halide emulsion is a magneta coupler represented by the following formula I ##STR1## wherein Z represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by the Z is allowed to have substituents; X represents a substituent capable of splitting off through the reaction thereof on the oxidation products of a color developing agent; and R represents hydrogen or a substituent.

This application is a continuation of application Ser. No. 51,606, filedApr. 23, 1993; which is a continuation of application Ser. No. 839,922,filed Feb. 21, 1992; which is a continuation of application Ser. No.366,302, filed Jun. 13, 1989; which is a continuation of applicationSer. No. 218,448, filed Jul. 11, 1988; which is a continuation ofapplication Ser. No. 850,586, filed Apr. 10, 1986, all now abandoned,which, in turn, claims the priority of Japanese Application 84759/85,filed Apr. 20, 1985.

BACKGROUND OF THE INVENTION

The present invention relates to a color photographic light-sensitivematerial for printing use and more particularly to the colorphotographic light-sensitive material for printing use which isexcellent in gradation characteristics.

Generally speaking, in a negative-positive type color photography, aphotographic object is photographed on a color negative film through acamera, so that a negative image may be produced. The resulting negativeimage is printed on a sheet of color printing paper by a printer, sothat a color print of the image may be produced to be a final object ofappreciation.

One of the essential factors in controlling the quality of such a colorprint as described above is the gradation characteristics of a colorprinting paper.

If the gradation characteristics of a color printing paper are improper,that is, for example, if the gradation of the paper is too hard, theimage printed out on the paper will lack the proper image representationespecially in the low and high density portions of the printed image;and if the gradation is too soft, the image printed out on the paperwill come out dull and fuzzy. The resulting color print came out ineither case is not satisfactory in quality.

A color print will not come out satisfactorily in quality even if onlythe gradation characteristics of a single silver halide emulsion layerare satisfactory. In a substractive color photography, the three colors,cyan, magenta and yellow, are to be well-balanced together from thehigh-light portions to the shadow portions of a scene.

For example, if the garadation in the high density portions of a magentacolor developing layer is relatively softer than those of the othercolor developing layers, the shadow portions of the layer will bechanged from black into greenish black, and if the gradation thereof isrelatively too harder, the shadow portion thereof will be changed intoredish black. Anyway, a poor color print in color reproductivity willcome out in either case. As described above, the gradationcharacteristics of a color photographic light-sensitive material forcolor printing use are indispensable from the viewpoints of both toneand color reproductivity. It is therefore demanded to develop atechnique capable of enjoying a proper gradation.

One of the most well-known techniques for controlling gradations is tochange an amount of silver to be coated on. This technique has such adisadvatage that a maximum density is varied, though this is the easiestway to control gradations. Therefore, this technique is merely used fora fine adjustment or the like.

Another well-known technique is that one and the same layer or separatelayers are added with a plurality of silver halide grains which areharder than those in a desired gradation and have the same colorsensitivity with and the different photographic sensitivity from eachother. This is a technique generally known in the art. According to thistechnique, it seems to be able to produce any gradation theoretically,however, when applying this technique practically to a commercialproduction, the practical applicability thereof is limited because ofthe restrictions in manufacturing facility and costs or the like. Anymanufacturing effect may be unable to enjoy if this technique is solelyused.

There are well-known gradation adjusting techniques to be used in aprocess of preparing a light-sensitive silver halide emulsion. Theyinclude, for example, a hardening technique in which a metal ion dopesuch as that of rhodium, iridium or the like is used in a physicallyripening process; a technique in which the conditions desired forproducing silver halide grains are suitably selected from, for example,a single-jet precipitation process that is suitable for making asoft-type emulsion double-jet precipitation process that is suitable formaking a hard-type emulsion and the values of pAg, pH and compositiondistribution of a silver halide each in producung grains; a technique inwhich the conditions desired for a chemical sensitization are selected;and the like. The desired gradation may be obtained by using theabove-mentioned techniques independently or in combination, however, inalmost all cases, the deteriorations will be caused in otherphotographic characteristics such as sensitivity, fog, reciprocity lawfailure, latent-image stability, pressure resistance, and the like, orin stability in manufacture, and it requires much trouble to find outthe satisfactory conditions in either case. The above-mentionedtechnique may display only a limited effect if it is put into practicaluse.

For producing colors in a subtractive color process with a silver halidephotographic light sensitive material including a color photographiclight sensitive material for printing use, there uses a yellow coupler,a magenta coupler and a cyan coupler capable of forming a yellow dyeimage, a magenta dye image and a cyan dye image respectively through acoupling reaction thereof to the oxidation products of an aromaticprimary amine color developing agent. A gradation may anyway be changedby selecting the kinds of the above-mentioned couplers or thesubstituents thereof, however, this technique is also difficult to putinto practical use, because of the undesirable changes caused in theorder characteristics of the light sensitive material, such as thespectral characteristics of the dye images, the stability of the dyeimages.

Further, there are, for example, a description of a technique forsoftening a high-light portion by selecting a suitable high boilingsolvent for a coupler in Japanese Patent O.P.I. Publication No.40550/1983; and another description of a gradation adjusting techniquein which a high boiling solvent is selected and a catechol derivative isused in Japanese Patent Application No. 213161/1984. In thesetechniques, it was found that some specific density area of somespecific emulsion layer was effectivly improved but the overallgradations, the gradation balance and the like were not satisfactorilyimproved, though the techniques did work anyhow.

After the inventors were devoted to their studies by making use of theabove-mentioned techniques, they found that they reached the reasonablysatisfiable levels of the gradations and the balance thereof as far asboth of a blue-sensitive emulsion layer and a red-sensitive emulsionlayer concerned, but they did not reach any satisfiable level inmatching with a green-sensitive emulsion layer. Resultantly, they failedto obtain any color photographic light sensitive material for printinguse which is satisfiable in gradation characteristics.

In the above-mentioned techniques, it was difficult to manufactureinexpensively and stably any color photographic light sensitive materialfor printing use which is excellent in gradation and other photographiccharacteristics, as described above.

SUMMARY OF THE INVENTION

It is an object of the invention to provide a color photographic lightsensitive material for printing use in which the gradationcharacteristics thereof are excellent.

Another object of the invention is to provide a color photographic lightsensitive material for printing use in which the colors thereof areproperly balanced from the high light portions to the shadow portionsthereof and the color reproducibility thereof is excellent.

A further object of the invention is to provide a color photographiclight sensitive material for printing use which can be manufacturedstably and inexpensively and is excellen in both of gradation and otherphotographic characteristics.

The above-mentioned objects of the invention can be achieved with acolor photographic light sensitive material for printing use comprisinga reflecting support bearing thereon a blue-sensitive silver halideemulsion layer, a green-sensitive silver halide emulsion layer and ared-sensitive silver halide emulsion layer; wherein a silver halideemulsion contained in the above-mentioned green-sensitive silver halideemulsion layer is a monodispersed silver halide emulsion and a couplercombined with the above-mentioned monodispersed silver halide emulsionis a magenta coupler represented by the following formula [I]: ##STR2##wherein Z represents a group of non-metal atoms necessary for forming anitrogen-containing heterocyclic ring, and any ring formed by the Z isallowed to have substituents; X represents a substituent capable ofsplitting off through a reaction thereof to the oxidation products of acolor developing agent; and R represents hydrogen or a substituent.

DETAILED DESCRIPTION OF THE INVENTION

The invention will now be described in detail.

In the magenta couplers relating to the invention represented by theabove-given Formula [I], ##STR3## wherein Z represents a group ofnon-metal atoms necessary for forming a nitrogen-containing heterocyclicring, and any ring formed by the abovegiven Z is allowed to havesubstituents; X represents a substituent capable of splitting offthrough the reaction thereof to the oxidation products of a colordeveloping agent; and R represents hyrogen or a substituent.

The substituents represented by the abovegiven R include, for example, ahalogen, an alkyl group, a cycloalkyl group, an alkenyl group, acycloalkenyl group, an alkynyl group, an aryl group, a heterocyclicgroup, an acyl group, a sulfonyl group, a sulfinyl group, a sulfonylgroup, a carbamoyl group, a sulfamoyl group, a cyano group, a spirocompound residual group, a cross linked hydrocarbon compound residualgroup, an alkoxy group, an aryloxy group, a heterocyclicoxy group, asiloxy group, an acyloxy group, a carbamoyloxy group, an amino group, anacylamino group, a sulfonamido group, an imido group, a ureido group, asulfamoylamino group, an alkoxycarbonylamino group, anaryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonylgroup, an alkylthio group, an arylthio group, and a heterocyclicthiogroup.

A halogen includes, for example, chlorine and bromine, and morepreferably among them, chlorine.

The alkyl groups represents by R include, for example, those each having1 to 32 carbon atoms and an alkenyl group; the alkynyl groupsrepresented thereby include, for example, those each having 2 to 32carbon atoms and a cycloalkyl group; and the cycloalkenyl groupsrepresented thereby include, for example, those each having 3 to 12carbon atoms and more preferably those each having 5 to 7 carbon atoms.The above-mentioned alkyl, alkenyl and alkynyl groups are allowed to benormal chained or branch chained.

The above-mentioned alkyl, alkenyl, alkynyl, cycloalkyl and cycloalkenylgroups are allowed to have such a substituent as an aryl group, a cyanogroup, a halogen, a heterocyclic group, a cycloalkyl group, acycloalkenyl group, a spiro compound residual group and a cross linkedhydrocarbon compound residual group. Besides the above, they are alsoallowed to have a substituent substituted through such a carbonyl groupas that of acyl carboxy, carbamoyl, alkoxycarbonyl or aryloxycarbonyl.They are further allowed to have such a substituent substituted througha hetero atom as, typically, those substituted through oxygen such asthat of hydroxy, alkoxy, aryloxy, heterocyclicoxy, siloxy, acyloxy,carbamoyloxy or the like; those substituted through nitrogen such asthat of nitro, amino including, for example, dialkylamino and the like,sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino,sulfonamido, imido, ureido or the like; those substituted through sulfursuch as that of alkylthio, aryltho, heterocyclicthio, sulfonyl,sulfinyl, sylfamoyl or the like; and those substituted throughphosphorus such as that of phosphonyl or the like.

The above-mentioned substituents typically include, for example, amethyl, ethyl, isopropyl, t-butyl, pentadecyl, heptadecyl, 1-hexylnonyl,1,1'-dipentylnonyl, 2-chloro-t-butyl, trifluoromethyl, 1-ethoxytridecyl,1-methoxyisopropyl, methanesulfonylethyl, 2,4-di-t-amylphenoxymethyl,anilino, 1-phenyl-isopropyl, 3-m-butanesulfonaminophenoxypropyl,3-4'-{α-[4"(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino}phenylpropyl,3-{4'-[α-(2",4"-di-t-amylphenoxy)butaneamido]phenyl}-propyl,4-[α-(o-chlorophenoxy)tetradecaneamidophenoxy]propyl, aryl, cyclopentyl,or cyclohexyl group.

The aryl groups represented by R preferably include, for example, aphenyl group, and they are allowed to have such a substituent as analkyl, alkoxy or acylamino group. They typically include, for example, aphenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecaneamidophenyl,hexadesiloxy phenyl, or 4'-[α-(4"-t-butylphenoxy)tetradecaneamido]phenylgroup.

The heterocyclic groups represented by R preferably include, forexample, the 5 to 7 membered ones. They are allowed to be substituted orcondensed, and they typically include, for example, a 2-furyl,2-thienyl, 2-pyrimidinyl, or 2-benzothiazolyl group.

The acyl groups represented by R include, for example, those of acetyl,phenylacetyl, dodecanoyl, alkylcarbonyl such asα-2,4-di-t-amylphenoxybutanoyl, benzoyl, 3-pentadecyloxy benzoyl,arylcarbonyl such as p-chlorobenzoyl, and the like.

The sulfonyl groups represented by R include, for example, analkylsulfonyl group such as methylsulfonyl and dodecylsulfonyl groups,an arylsulfonyl group such as benzenesulfonyl and p-toluenesulfonylgroups.

The sulfinyl groups represented by R include, for example, analkylsulfinyl group such as an ethylsulfinyl, octylsulfinyl or3-phenoxybutylsulfinyl group; an arylsulfinyl group such as aphenylsulfinyl or m-pentadecylphenylsulfinyl group.

The phosphonyl groups represented by R include, for example, analkylphosphonyl group such as butyloctylphosphonyl group, analkoxyphosphonyl group such as octyloxyphosphonyl group, anaryloxyphosphonyl group such as phenoxyphosphonyl group, anarylphosphonyl group such as phenylphosphonyl group, and the like.

In the carbamoyl groups represented by R, the alkyl, aryl and morepreferably phenyl groups thereof may be substituted. They include, forexample, N-methylcarbamoyl group, N,N-dibtylcrbamoyl group,N-(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoylgroup, N-{3-(2,4-di-t-amylphenoxy)propyl}carbamoyl group, and the like.

In the sulfamoyl groups represented by R, the alkyl, aryl and morepreferably phenyl groups may be substituted. They include, for example,N-propylsulfamoyl group, N,N-diethylsulfamoyl group,N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoylgroup, N-phenylsulfamoyl group, and the like.

The spiro compound residual groups represented by R include, forexample, spiro[3.3]heptane-1-yl, and the like.

The cross linked hydrocarbon compound residual groups include, forexample, bicyclo[2.2.19 heptane-1-yl, tricyclo [3.3.1.1³,7 ]decane-1-yl,7,7-dimethyl-bicyclo[2.2.1]heptane-1-yl and the like.

The alkoxy groups represented by R are allowed to substitute thesubstituents given to the above-mentioned alkyl groups, and theyinclude, for example, a methoxy, propoxy, 2-ethoxyethoxy, pentadecyloxy,2-dodecyloxyethoxy, phenthyloxyethoxy and the like groups.

The aryloxy groups represented by R preferably include, for example, aphenyloxy group, and the aryl nucleus thereof is further allowed to besubstituted by the substituents or atoms given to the above-mentionedaryl groups. They include, for example, a phenoxy, p-t-butylphenoxy,m-pentadecylphenoxy and the like groups.

The heterocyclicoxy groups represented by R preferably include, forexample, those each having a 5 to 7 membered heterocyclic ring which isalso allowed to have a substituent. They include, for example, a3,4,5,6-tetrahydropyranyl-2-oxy group and a 1-phenyltetrazole-5-oxygroup.

The siloxy groups represented by R may further be substituted by analkyl group or the like. They include, for example, a trimethylsiloxy,triethylsiloxy, dimethylbutylsiloxy and the like groups.

The acryloxy groups represented by R include, for example, analkylcarbonyloxy, arylcarbonyloxy and the like groups. They are furtherallowed to have a substituent including, typically, an acetyloxy,α-chloracetyloxy, benzoyloxy and the like groups.

The carbamoyloxy groups represented by R may be substituted by an alkyl,aryl or the like group. They include, for example, N-ethylcarbamoyloxy,N,N-diethylcarbamoyloxy, N-phenylcarbamoyloxy and the like group.

The amino groups represented by R may also be substituted by an alkylgroup, an aryl group and more preferably a phenyl group, and the likegroup. They include, for example, an ethylamino, anilino,m-chloroanilino, 3-pentadecyloxycarbonylanilino,2-chloro-5-hexadecaneamidoanilino and the like groups.

The acylamino groups represented by R include, for example, analkylcarbonylamino, arylcarbonylamino and more preferablyphenylcarbonylamino, and the like groups. They may further have asubstituent including, typically, an acetamido, α-ethylpropaneamido,N-phenylacetamido, dodecaneamido, 2,4-di-t-amylphenoxyacetamido,α-3-t-butyl-4-hydroxyphenoxybutaneamido and the like groups.

The sulfonamido groups represented by R include, for example, analkylsulfonylamino, arylsulfonylamino and the like groups, and they areallowed to have a substituent including, typically, amethylsulfonylamino, pentadecylsulfonylamino, benzenesulfonamido,p-toluenesulfonamido, 2-methoxy-5-t-amylbenzenesulfonamido and the likegroups.

The imido groups represented by R may be of the open-chained or of thecyclic, and they may also have a substituent including, for example, asuccinic acid imido, 3-heptadecyl succinic acid imido, phthalic imido,glutaric imido and the like groups.

The ureido groups represented by R may be substituted by an alkyl, aryland preferably phenyl or the like group. They include, for example,N-ethylureido, N-methyl-N-decylureido, N-phenylureido, N-p-tolylureidoand the like groups.

The sulfamoylamino groups represented by R may be substituted by analkyl, aryl and more preferably phenyl, or the like group. They include,for example, a N,N-dibutylsulfamoylamino, N-methylsulfamoylamino,N-phenylsulfamoylamino and the like groups.

The alkoxycarbonylamino groups represented by R may further have asubstituent including, for example, a methoxycarbonylamino,methoxyethoxycarbonylamino, octadecyloxycarbonylamino and the likegroups.

The aryloxycarbonylamino groups represented by R may have a substituentincluding, for example, a phenoxycarbonylamino,4-methylphenoxycarbonylamino and the like groups.

The alkoxycarbonyl groups represented by R may further have asubstituent including, for example, a methoxycarbonyl, butyloxycarbonyl,dodecyloxycarbonyl, octadecyloxycarbonyl, ethoxymethoxycarbonyloxy,benzyloxycarbonyl and the like groups.

The aryloxycarbonyl groups represented by R may further have asubstituent including, for example, a phenoxycarbonyl,p-chlorophenoxycarbonyl, m-pentadecyloxyphenoxycarbonyl and the likegroups.

The alkylthio groups represented by R may further have a substituentincluding, for example, an ethylthio, dodecylthio, octadecylthio,phenethylthio and 3-phenoxypropylthio groups.

The arylthio groups represented by R include preferably a phenylthiogroup and may further have a substituent including, for example, aphenylthio, p-methoxyphenylthio, 2-t-octylphenylthio,3-octadecylphenylthio, 2-carboxyphenylthio, p-acetaminophenylthio andthe like groups.

The heterocyclicthio groups represented by R include, preferably, a 5 to7 membered heterocyclicthio group, and may further have a condensed ringor a substituent. They include, for example, a 2-pyridylthio,2-benzothiazolylthio, and 2,4-diphenoxy-1,3,5-triazole-6-thio groups.

The substituents represented by X which are capable of splitting offthrough the reaction thereof to the oxidation products of a colordeveloping agent include, for example, the groups substituted throughcarbon, oxygen, sulphur or nitrogen atom as well as such a halogen atomas chlorine, bromine, fluorine or the like atom.

The groups substituted through a carbon atom include, for example, acarboxyl group and besides, the groups represented by the followingformula: ##STR4## wherein R_(1') is synonymous with the above-mentionedR; Z' is synonymous with the above-mentioned Z; and R_(2') and R_(3')represent hydrogen, an aryl group, an alkyl group or a heterocyclicgroup, respectively; a hydroxymethyl group and a triphenylmethyl group.

The groups substituted through oxygen include, for example, an alkoxy,aryloxy, heterocyclicoxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy,aryloxycarbonyloxy, alkyloxalyloxy and alkoxyoxalyloxy groups.

The alkoxy groups are allowed to have a substituent including, forexample, an ethoxy, 2-phenoxyethoxy, 2-cyanoethoxy, phenethylopxy,p-chlorobenzyloxy and the like groups.

Among the aryloxy groups, a phenoxy group is preferred. Such aryloxygroups may have a substituent. They include typically phenoxy,3-methylphenoxy, 3-dodecylphenoxy,4-methanesulfonamidophenoxy,4-[α-(3'-pentadecylphenoxy)butanamido]phenoxy,hexyldecyl- carbamoylmethoxy, 4-cyanophenoxy, 4-methanesulfonylphwnoxy,1-naphthyloxy, p-methoxyphenoxy and the like groups.

The hetero cyclicoxy groups include preferably a 5 to 7 memberedheterocyclicoxy group, and may have a substituent. They typicallyinclude a 1-phenyltetrazolyloxy, 2-benzothiazolyloxy or the like group.

The acyloxy groups include, for example, such an alkylcarbonyloxy groupas an acetoxy, butanoloxy or the like group; such an alkenylcarbonyloxygroup as a cinnamoyloxy group; ans such an arylcarbonyloxy group as abenzoyloxy group.

The sulfonyloxy groups include, for example, a butanesulfonyloxy groupor a methanesulfonyloxy group.

The alkonylcarbonyloxy groups include, for example, an ethoxycarbonyloxygroup or a benzyloxycarbonyloxy group.

The aryloxycarbonyl groups include, for example, a phenoxycarbonyloxygroup or the like groups.

The alkyloxalyloxy groups include, for example, a methyloxalyloxy group.

The alkoxyoxalyloxy groups include, for example, an ethoxyoxalyloxygroup and the like.

The groups substituting through sulphur include, for example, analkylthio, arylthio, heterocyclicthio, alkyloxythiocarbonylthio or thelike groups.

The alkylthio groups include, for example, a butylthio,2-cyanoethylthio, phenethylthio, benzylthio or the like groups.

The arylthio groups include, for example, a phenylthio,4-methanesulfonamidophenylthio, 4-dodecylphenethylthio,4-nonafluoropentanamidophenethylthio, 4-carboxyphenylthio,2-ethoxy-5-t-butylphenylthio or the like groups.

The heterocyclicthio groups include, for example, a1-phenyl-1,2,3,4-tetrazolyl-5-thio, 2-benzothiazolylthio or the likegroups.

The alkyloxythiocarbonylthio groups include, for example, adodecyloxythiocarbonylthio or the like groups.

The groups sustituting through the above-mentioned nitrogen include, forexample, those represented by the following formula: ##STR5## wherein,R_(4') and R_(5') represent hydrogen, an alkyl, aryl, heterocyclic,sulfamoyl, carbamoyl, acyl, sulfonyl, aryloxycarbonyl or alkoxycarbonylgroup; and R_(4') and R_(5') may be so coupled each other as to form aheterocyclic ring, provided that R_(4') and R_(5') shall not be hydrogenat the same time.

The alkyl groups are allowed to be normal-chained or branch-chained andpreferably have 1 to 24 carbon atoms. The alkyl groups may have such asubstituent as an aryl, alkoxy, aryloxy, alkylthio, arylthio,alkylamino, arylamino, acylamino, sulfonamido, imino, acyl,alkylsulfonyl, arylsulfonyl, carbamoyl, sulfamoyl, alkoxycaronyl,aryloxycarbonyl, alkyloxycarbonylamino, aryloxycarbonylamino, hydroxyl,carboxyl and cyano groups and a halogen. As for the typical examples ofthe alkyl groups, ethyl, 2-ethylhexyl and 2-chlorethyl groups may begiven.

It is preferred that the aryl groups represented by R_(4') and R_(5')have 6 to 32 carbon atoms and that they are a phenyl or naphthyl groupin particular. They are also allowed to have substituents including, forexample, the substituents to the alkyl groups represented by theabove-mentioned R_(4') and R_(5'), and an alkyl group. The typicalexamples of the aryl groups include a phenyl, 1-naphthyl or4-methylsulfonylphenyl group.

It is preferred that the heterocyclic groups represented by theabove-mentioned R_(4') and R_(5') are the 5 to 6 membered ones. They arealso allowed to be of the condensed ring and to have a substituent. Thetypical examples thereof include a 2-furyl, 2-quinolyl, 2-pyrimidyl,2-benzothiazolyl, 2-pyridyl or the like groups.

The sulfamoyl groups represented by the R_(4') and R_(5') include, forexample, N-alkylsulfamoyl, N,N-dialkylsulfamoyl, N-arylsulfamoyl,N,N-diarylsulfamoyl and the like groups. These alkyl and aryl groups areallowed to have the same substituents as those given in the cases of theabove-mentioned alkyl and aryl groups. The typical examples of thesulfamoyl groups include N,N-diethylsulfamoyl, N-methylsulfamoyl,N-dodecylsulfamoyl and N-p-tolylsulfamoyl groups.

The carbamoyl groups represented by the R_(4') and R_(5') include, forexample, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, N-arylcarbamoyl,N,N-diarylcarbamoyl and the like groups. These alkyl and aryl groups areallowed to have the same substituents as those given in the cases of theabove-mentioned alkyl and aryl groups. The typical examples of thecarbamoyl groups include N,N-diethylcarbamoyl, N-methylcarbamoyl,N-dodecylcarbamoyl, N-p-cyanophenylcarbamoyl and N-p-tolylcarbamoylgroups.

The acyl groups represented by the R_(4') and R_(5') include, forexample, alkylcarbonyl, arylcarbonyl and heterocyclic carbonyl groups.Such alkyl, aryl and heterocyclic groups are allowed to have asubstituent. The typical examples of the acyl groups include ahexafluorobutanoyl, 2,3,4,5,6-pentafluorobenzoyl, acetyl, benzoyl,naphthoyl, 2-fulylcarbonyl or the like groups.

The sulfonyl groups represented by the R_(4') and R_(5') include, forexample, an alkylsulfonyl, arylsulfonyl or heterocyclic sulfonyl group,and they are also allowed to have a substitutent. The typical examplesof these sulfonyl groups include an ethanesulfonyl, benzenesulfonyl,octanesulfonyl, naphthalenesulfonyl, p-chlorobenzenesulfonyl or the likegroups.

The aryloxycarbonyl groups represented by the R_(4') and R_(5') areallowed to have the same substituents as those given in the case of theabove-mentioned aryl groups. The typical examples thereof include aphenoxycarbonyl group and the like.

The alkoxycarbonyl groups represented by the R_(4') and R_(5') areallowed to have the same substituents as those given in the case of theabove-mentioned alkyl groups. The typical examples thereof include amethoxycarbonyl, dodecyloxycarbonyl, benzyloxycarbonyl or the likegroups.

It is preferred that the above-mentioned heterocyclic rings formed bycoupling R_(4') or R_(5') thereto are the 5 to 6 membered ones. They maybe saturated or unsaturated and of the aromatic or the non-aromatic andfurther condensed rings. Such heterocyclic rings include, for example,N-phthalimido, N-succinic acid imido, 4-N-urazolyl, 1-N-hydantoinyl,3-N-2,4-dioxooxazolidinyl, 2-N-1,1-dioxo-3-(2H)-oxo-1,2-benzothiazolyl,1-pyrrolyl, 1-pyrrolidinyl, 1-pyrazolyl, 1-pyrazolidinyl, 1-piperidinyl,1-pyrrolinyl, 1-imidazolyl, 1-imidazolinyl, 1-indolyl, 1-isoindolinyl,2-isoindolyl, 2-isoindolinyl, 1-benzotriazolyl, 1-benzoimidazolyl,1-(1,2,4-triazolyl), 1-(1,2,3-triazolyl), 1-(1,2,3,4-tetrazolyl),N-morpholinyl, 1,2,3,4-tetrahydroquinolyl, 2-oxo-1-pyrrolidinyl,2-1H-pyridone, 2-oxo-1-piperidinyl and the like groups. Theseheterocyclic groups may also be substituted by an alkyl, aryl, alkyloxy,aryloxy, acyl, sulfonyl, alkylamino, arylamino, acylamino, sulfonamino,carbamoyl, sulfamoyl, alkylthio, arylthio, ureido, alkoxycarbonyl,aryloxycarbonyl, imido, nitro, cyano, carboxyl or the like groups, ahalogen or the like.

The nitrogen-containing heterocyclic rings formed by the above-mentionedZ or Z' include, for example, a pyrazole, imidazole, triazole, tetrazoleor the like ring. The substituents which the above-mentioned rings areallowed to have include, for example, the same substituents as thosegiven with respect to the above-mentioned R.

In the case that such a substituent as R or one of from R₁ to R₈ on aheterocyclic ring shown in Formula [I] and Formulae [II] to [VIII] ofwhich will be described later has the following part; ##STR6## (wherein,R", X and Z" are synonymous with R, X and Z in Formula [I]), a so-calledbis-type coupler is formed, and it is a matter of course that suchcouplers shall be included in the invention. Further, a ring formed bythe Z, Z', Z" or Z₁ that is to be described later, it is also allowedthat another ring such as a 5 to 7 membered cycloalkene may becondensed. In Formula [VI], for example, it is allowed to form a ringsuch as a 5 to 7 membered cycloalkene or benzene by coupling R₇ and R₈to each other.

The magenta couplers represented by Formula [I] may further typically berepresented by the following formulae [II] to [VII]: ##STR7##

In the abovegiven Formulae [II] to [VII], R₁ to R₈ and X are synonymouswith the aforementioned R and X, respectively.

The couplers represented by the following Formula [VIII] are thepreferred ones among those represented by the Formula [I]; ##STR8##wherein R₁, X and Z₁ are synonymous with R, X and Z denoted in theFormula [I].

The particularly preferred magenta couplers among those represented bythe abovegiven Formulae [II] to [VII] are the magenta couplersrepresented by Formula [II].

A substituent on the heterocyclic rings in the Formulae [I] to [VIII]becomes a preferred one, provided that R in Formula [I] or R₁ inFormulae [II] to [VIII] satisfies the following requirement 1. Itbecomes a further preferred one, provided that the R or R₁ satisfies thefollowing requirements 1 and 2. It becomes a particularly preferred one,provided that the R and R₁ satisfies the following requirements 1, 2 and3:

Requirement 1: An atom directly coupled to a heterocyclic ring is acarbon atom.

Requirement 2: Only one hydrogen atom couples to the carbon atom, ornothing couples thereto.

Requirement 3: Every coupling of the carbon atom to the neighboringatoms is a single coupling.

The most preferred substituents R and R₁ on the above-mentionedheterocyclic rings are represented by the following Formula [IX];##STR9## wherein R₉, R₁₀ and R₁₁ represent, respectively, hydrogen, ahalogen, an alkyl group, cycloalkyl group, alkenyl group, cycloalkenylgroup, alkynyl group, aryl group, heterocyclic group, acyl group,sulfonyl group, sulfinyl group, sulfonyl group, carbamoyl group,sulfamoyl group, cyano group, spiro compound residual group,cross-linked hydrocarbon compound residual group, alkoxy group, aryloxygroup, heterocyclicoxy group, siloxy group, acyloxy group, carbamoyloxygroup, amino group, acylamino group, sulfonamido group, imido group,ureido group, sulfamoylamino group, alkoxycarbonylamino group,aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group,alkylthio group, arylthio group or heterocyclicthio group; and at leasttwo of the R₉, R₁₀ and R₁₁ are not hydrogen.

Two out of the above-mentioned R₉, R₁₀ and R₁₁ which are, for example,R₉ and R₁₀ are allowed to couple to each other so as to form a saturatedor unsaturated ring such as a cycloalkane, cycloalkene or heterocyclicring, or so as further to produce a cross-linked hydrocarbon compoundresidual group by coupling R₁₁ to the above-mentioned ring.

The groups represented by R₉ to R₁₁ are allowed to have a substituent.The typical examples of both the groups represented by R₉ to R₁₁ and thesubstituents which the above-mentioned groups are allowed to haveinclude the typical examples of the groups represented by R denoted inthe above-given Formula [I] and the substituents thereto.

The typical examples of both the rings formed by coupling, for example,R₉ and R₁₀ to each other and the cross-linked hydrocarbon compoundsformed by R₉ to R₁₁, and the examples of the substituents which thegroups represented by R₉ to R₁₁ are allowed to have include the typicalexamples of a cycloalkyl group, a cycloalkenyl group, a heterocyclicgroup and a cross-linked hydrocarbon compound residual group eachrepresented by R denoted in the aforegiven Formula [I] and thesubstituents thereto.

The following two cases are preferred with respect to the Formula [IX]:

i) A case that two of R₉ through R₁₁ are alkyl groups, and

ii) Another case that one of the R₉ through R₁₁ is hydrogen and, R₁₀ andR₁₁ are coupled to each other so as to form a cycloalkyl group, togetherwith the carbon atom.

Further, in the case i), the preferable case is that two of R₉ throughR₁₁ are alkyl groups and the rest is either hydrogen or an alkyl group.

The above-mentioned alkyl and cycloalkyl groups are allowed to have asubstituent. The typical examples of the alkyl groups, the cycloalkylgroups and the subsituents include the typical examples of the alkylgroups, the cycloalkyl groups and the substituents represented by Rdenoted in the aforegiven Formula [I].

For serving as the substituents which both of the rings formed by Zdenoted in Formula [I] and those formed by Z₁ denoted in Formula [VIII]are allowed to have, and as R₂ through R₈ denoted in Formula [II]through [VI], the preferred ones are represented by the followingFormula [X]; ##STR10## wherein R¹ represents an alkylene group; and R²represents an alkyl, cycloalkyl or aryl group.

The alkylene group represented by R¹ is to have prepferably not lessthan 2 carbon atoms and more preferably 3 to 6 carbon atoms in thenormal chained portion thereof, regardless of the normal or branchchained. The alkylene group may also have a substituent.

The examples of the above-mentioned substituents include those which analkyl group may have provided that the alkyl group is represented by Rdenoted in the aforegiven Formula [I].

The preferred substituents include, for example, a phenyl group.

The typical and preferable examples of the alkylene groups representedby R¹ are given below: ##STR11##

It is regardless of that the alkyl groups represented by R² are normalchained or branch chained.

The above-mentioned alkyl groups typically include a methyl, ethyl,propyl, isopropyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl,hexadecyl, octadecyl, 2-hexyldecyl or the like group.

The cycloalkyl groups represented by R² preferably include a 5 to 6membered one that is, for example, a cyclohexyl group.

The alkyl and cycloalkyl groups each represented by R² are allowed tohave a substituent which includes, for example, the substituents to theabove-mentioned R¹.

The typical examples of the aryl groups represented by R² include, forexample, a phenyl group and a naphthyl group. The aryl groups areallowed to have a substituent. These substituents include, for example,a normal chained or branch-chained alkyl group and, besides, thesubstituents exemplified as those to the above-mentioned R¹.

When there are not less than two substituents, such substituents may bethe same with or the different from each other.

The particularly preferable compounds among those represented by Formula[I] are represented by the following Formula [XI]; ##STR12## wherein Rand X are synonymous with R and X denoted in Formula [I]; and R¹ and R²are synonymous with R¹ and R² denoted in Formula [X]. ##STR13##

The above-mentioned typical couplers were synthesized by referring to`Journal of the Chemical Society, Perkin I`, 1977, pp. 2047-2052; U.S.Pat. No. 3,725,067; Japanese Patent O.P.I. Publication Nos. 99437/1984and 42045/1983; and the like.

The couplers of the invention may ordinarily be used in an amount offrom 1×10⁻³ mole to 1 mole, and more preferably from 1×10⁻² mole to8×10⁻¹ mole, per mole of a silver halide.

The couplers of the invention may also be used together with the otherkinds of magenta couplers.

In the invention, the expression, `A magenta coupler combined with asilver halide emulsion layer`, means `a magenta coupler capable offorming a magenta dye-image through a reaction thereof upon theoxidation products of a color developing agent produced incolor-developing the silver halide emulsion layer`.

Next, a monodispersed emulsion relating to the invention will now bedescribed.

The monodispersed emulsions relating to the invention mean those havinga variation coefficient of not more than 0.22 and more preferably notmore than 0.15 in the grain size distribution of a silver halide in theemulsion. A variation coefficient indicates an extent of the grain sizedistribution and is determined by the following equations: ##EQU1##wherein ri represents the grain size of individual grains; and nirepresents the number thereof.

The term, grain size, denoted herein means the diameter of a grain whenthe grain is of a globular-shaped silver halide, and it also means thediameter of a circular image having the same area as that of theprojected grain image when the grain is that in the shapes other thanthe globular shape.

The monodispersed emulsions relating to the invention may be usedindependently or in combination in the form of mixture, provided thatthe variation coefficients thereof are not more than 0.22. It is alsoallowed to use the mixture of a polydispersed emulsion and amonodispersed emulsion. The preferable monodispersed emulsions relatingto the invention include, for example, a single kind of or a mixture ofnot more than three kinds of monodispersed emulsions each having theabove-mentioned variation coefficient of not more than 0.22, or amixture of a polydispersed emulsion and a monodispersed emulsion. In thecase of the above-mentioned mixture, the monodispersed emulsion has anaverage grain size smaller than that of the polydispersed emulsion andoccupies not less than 40% of a total projected area of the whole of thesilver halide grains. More preferably, the monodispersed emulsionrelating to the invention comprises a single kind of a monodispersedemulsion having the above-mentioned variation coefficient of not morethan 0.22 or a mixture of the two kinds thereof.

In the silver halide grains used in the monodispersed emulsions relatingto the invention (hereinafter called the emulsions of the invention),the average grain size thereof defined by the above-mentioned formula ispreferably from not smaller than 0.25 μm to not larger than 0.75 μm and,more preferably, from not smaller than 0.35 μm to not larger than 0.65μm.

There is no particular limitation to the silver halide composition of asilver halide grain to be used in the emulsion of the invention. It is,however, preferred that the silver iodide contents are small, that is,the emulsion is a silver chlorobromide emulsion, substantially. Thesubstantial silver chlorobromide emulsion means that the silver halideof a silver halide grain used in a silver halide emulsion is composed ofsilver iodide less than 1 mol % and, silver chloride and silver bromidefor the rest.

In a silver halide grain, a silver chloride content is preferably notless than 5 mol % and, more preferably, not less than 15 mol %.

Any crystal habits of the silver halide grains may be used in theemulsions of the invention. Any regular formed and irregular formedcrystals including those in the globular or plate form may be used. Inthese grains, there may be used the crystals having any ratios of {100}plane to {111} plane. In addtion to the above, those in the compoundcrystal forms and those mixed with various crystal formed grains mayeither be used.

The silver halide grains to be used in the emulsions of the inventionmay be prepared in any one of the acid process, neutral process andammonia process. It is allowed to grow such grains either at a time orafter producing seed grains. The respective processes of preparing theseed grains and of growing them may be the same with or the differentfrom each other.

The processes for reaction of a soluble silver salt and a soluble halidemay include a normal precipitation process (or single-jet precipitationprocess), a reverse precipitation process, a double-jet precipitationprocess, the combination thereof and the like. Among them, thedouble-jet precipitation process is preferred for the reaction. Further,with the purpose of improving the monodispersibility a pAg-controlleddouble-jet precipitation process described in Japanese Patent O.P.I.Publication No. 48521/1979 may also be used as a version of theabove-mentioned double-jet processes.

If further required, such a solvent for silver halides as thioether orsuch a crystal habit controlling agent as a mercapto-group-containingcompound and a spectral sensitizer may also be used.

In course of forming and/or growing the silver halide grains used in theemulsions of the invention, a metal ion may be added to and contained inthe inside and/or surface of the grain by the use of a cadmium salt, azinc salt, a lead salt, a tarium salt, an iridium salt or the complexsalts thereof, a rhodium salt or the complex salts thereof, or an ironsalt or the complex salts thereof; and a reduction sensitization speckmay be provided to the inside and/or surface of the grain by putting thegrain in a suitable reducible atmosphere.

In the emulsions of the invention, unnecessary soluble salts may beremoved therefrom after completing the growth of the silver halidegrains, or the unnecessary soluble salts may remain unremoved. If theyare to be removed, it can be done according to the process described inResearch Disclosure, vol. 17643.

In the silver halide grains used in the emulsions of the invention, theinside and the surface thereof may be composed of the same layer or thedifferent layers.

The silver halide grains used in the emulsions of the invention may bethose in which a latent image may be formed mainly on the surfacethereof, or formed mainly inside the grains.

The emulsions of the invention are chemically sensitized in the usualmanner. Namely, they may be applied with a sulfur sensitization processusing a sulfur-containing compound capable of reacting upon a silver ionand an active gelation; a selenium sensitization process using aselenium compound; a reduction sensitization process using a reduciblesubstance; or a noble-metal sensitization process using gold or othernoble metal compounds, independently or in combination.

The emulsions of the invention may be spectrally sensitized to thedesired wavelength region by making use of the dyes which are well-knownin the photographic industry as the spectral sensitizers. These spectralsensitizers may be used independently or in combination. Further, theemulsions of the invention are allowed to contain, as well as thespectral sensitizers, a dye having no spectral sensitizing function initself or a supersensitizer which is a compound not substantiallyabsorbing visible rays of light and capable of increasing thesensitizing function of the spectral sensitizers.

With the purposes of preventing a light-sensitive material from causinga fog and/or of keeping the photographic characteristics thereof stablein manufacture, preservation or photographic processing of thelight-sensitive material, it is allowed to add the compounds well-knownin the photographic industry as an antifoggant or a stabilizer into theemulsions of the invention, at any point of time when the chemicalsensitization process is being carried out and/or completed, and/or anytime thereafter, but before the silver halide emulsion is coated on.

`Color photographic light-sensitive materials for printing use` embodiedin the invention mean the color light-sensitive materials suitable forthe purpose of direct appreciation. Accordingly, they shall not belimited only to a light-sensitive material using paper to serve as thesupport thereof. For example, there may be used a baryta paper, a papersupport coated with a polyolefin resin and the like, apolyethylene-terephthalate support containing white pigment, a supportcomprising a transparent film base bearing thereon a hydrophiliccolloidal layer into which a white pigment is dispersively added, andthe like. Namely, the preferable supports to be used in the colorphotographic light-sensitive materials of the invention are those inwhite.

The preferable supports include, for example, a paper support coatedthereon with a polyolefin resin added with a white pigment such as ananatase type titanium dioxide, a polyethyleneterephthalate filmcontaining a white pigment such as barium sulfate.

About the reason why the effects of the invention can remarkably bedisplayed only on the color photographic light-sensitive materials forprinting use which has the above-mentioned reflection type supports, itstill remains unexplained. There may supposedly be some reasons such asan optical or psychological reason from the special characteristics thata white-colored support is used to appreciated a color photographdirectly with reflected light, a physiological reason that magenta coloris rather prominent than the other colors, that is, the spectralluminous efficiency of the magenta color is high, and the like.Nevertheless, these reasons have not yet definitely answered to theeffects of the invention.

As for the binders or the protective colloids to be used in the colorphotographic light-sensitive materials for printing use relating to theinvention, a gelatin is advantageously used and, besides, a gelatinderivative, a graft-polymer of gelatin and other macromolecularsubstances, a protein, a sugar derivative, a cellulose derivative, ahydrophilic colloid such as a mono- or co-polymer synthesizedhydrophilic macromolecular substance and the like.

In the color photographic light-sensitive materials for printing userelating to the invention, the photographic emulsion layers and theother hydrophilic colloidal layers thereof are hardened bycross-coupling thereto a binder molecule or a protective colloid and byusing therein some hardeners for hardening the layer strengthindependently or in combination. It is preferred to add such a hardenerin an amount of the order than another hardener is not needed to addfurther to a processing solution but the light-sensitive material may behardened. It is the matter of course that such hardeners may be addedinto the processing solutions.

In the color photographic light-sensitive materials for printing userelating to the invention, a plasticizer may also be added tot he silverhalide emulsions and/or the other hydrophilic colloidal layers thereof,with the purpose of increasing the flexibility of such layers.

In the color photographic light-sensitive materials for printing userelating to the invention, the photographic emulsion layers and theother hydrophilic colloidal layers thereof are allowed to contain anon-water-soluble or hardly soluble synthetix polymer disposed matter (alatex), with the purpose of improving the dimentional stability of suchlayers or the like.

In the color photographic light-sensitive materials for printing userelating to the invention, the emulsion layers thereof are processingfor color development by making use of a dye-forming coupler for forminga dye through a coupling reaction on the oxidation products of anaromatic primary amine developer such as a p-phenylenediaminederivative, an Aminophenol derivative or the like. It is an ordinarymanner to select the suitable ones from the dye-forming couplers so asto form the dyes capable of absorbing the respective spectra of thecorresponding emulsion layers; that is to say, a yellow dye-formingcoupler is selected therefrom to be used in a blue-sensitive emulsionlayer, a magenta one in a green-sensitive emulsion layer, and a cyan onein a red-sensitive emulsion layer, respectively. However, it is alsoallowed to prepare such emulsion layer in the different manner from theabove-mentioned combinations in accordance with the purposes.

The yellow dye-forming couplers include, for example, an acylacetamidecoupler such as those of a benzoylacetanilide or a pivaloylacetanilide;the magenta dye-forming couplers include, for example, a 5-pyrazolonecoupler, a pyrazolobenzimidazole coupler, a pyrazolotriazole coupler, anopen-chained acylacetonitrile coupler and the like; and the cyandye-forming couplers include, for example, a naphthol coupler, a phenolcoupler and the like.

The yellow-dye image-forming couplers typically include, for example, a4- or 2-equivalent coupler of acyacetamide type or bezoylmethan type;and they are described in, for example, U.S. Pat. Nos. 2,186,849,2,322,027, 2,728,658, 2,875,057, 3,265,506, 3,277,155, 3,408,194,3,415,652, 3,447,928, 3,664,841, 3,770,446, 3,778,277, 3,849,140 and3,894,875; British Patent Nos. 778,089, 808,276, 875,476, 1,402,511,1,421,126, and 1,513,832; Japanese Patent Examined Publication No.13576/1974; and Japanese Patent O.P.I. Publication Nos. 29432/1973,66834/1973, 10736/1974, 122335/1974, 28834/1975, 132926/1975,138832/1975, 3631/1976, 17438/1976, 26038/1976, 26039/1976, 50734/01976,53825/1976, 75521/1975, 89728/1976, 102636/1976, 107137/1976,117031/1976, 122439/1976, 143319/1976, 9529/1978, 82332/1978,135625/1978, 145619/1978, 23528/1979, 48541/1979, 65035/1979,133329/1979, and 598/1980.

The cyan-dye image-forming couplers typically include, for example, a 4-or 2-equivalent cyan-dye image-forming coupler of phenol or naphtholtype; and they are described in, for example, U.S. Pat. Nos. 2,306,410,2,356,475, 2,362,598, 2,367,531, 2,369,929, 2,423,730, 2,474,293,2,476,008, 2,498,466, 2,545,687, 2,728,660, 2,772,162, 2,895,826,2,976,146, 3,002,836, 3,419,390, 3,466,622, 3,476,563, 3,737,316,3,758,308, and 3,839,044; British Patent Nos. 478,991, 945,542,1,084,480, 1,377,233, 1,388,024 and 1,543,040; and Japanese PatentO.P.I. Publication Nos. 34725/1972, 10135/1975, 25228/1075, 112038/1975,117422/1975, 130441/1975/ 6551/1976, 37647/1976, 52828/1976,108841/1976, 109630/1978, 48237/1979, 66129/1979, 131931/1979 and32071/1980.

It is desired that the above-mentioned dye-forming couplers are to have,inside the moleculars thereof, the so-called ballast groups each ofwhich has not less than 8 carbon atoms and is capable of non-diffusingany coupler.

These dye-forming couplers may be either one of a 4-equivalent one inwhich four silver ions are necessarily reduced and a 2-equivalent one inwhich two silver ions are necessarily reduced, both for forming onemolecule dye. Among them, however, the 2-equivalent ones areparticularly preferred.

A solid dispersion process, a latex dispersion process, an oil-dropin-water type emulsion dispersion process and other various processesmay be applied to the hydrophobic compounds of the dye-forming couplersnot needed to be adsorbed on the surfaces of a silver halide crystal.These processes may suitably be selected to apply in accordance with thechemical structure and the like of the hydrophobic compounds of thesecouplers. In the oil-drop in-water type emulsion dispersion process,there may be applied with a process of dispersing the hydrophobiccompounds of the couplers or the like. In the process, generally, ahigh-boiling organic solvent having a boiling point of not lower than150° C. is dissolved in combination, if necessary, with a low boilingand/or water-soluble organic solvent; and the resulting solution isemulsified and dispersed together with a hydrophilic binder such as anaqueous gelatin solution containing a surface active agent by making useof such a dispersing means as a stirrer, homogenizer, colloid-mill,flow-jet mixer, supersonic device or the like; and, after then, theresulting emulsified and dispersed matter is added to a directinghydrophilic colloidal layer.

The high-boiling organic solvents to be used in the magenta couplersrepresented by the aforegiven Formula [I] relating to the invention arepreferred to be a compound of less than 0.6 in dielectric constant. Thelower limit of the dielectric constant is not particularly limited, buta dielectric constant of not less than 1.9 is preferred. The preferredcompounds include, for example, such an ester as a phthalate, phosphateand the like, an organic acid amide, a ketone, a hydrocarbon compound,and the like, each having a dielectric constant of less than 6.0; andamong them, the more preferable ones are the phthalate or the phosphate.Further, the above-mentioned organic solvents may be a mixture of notless than two of them, and in this case the dielectric constant thereofis preferably less than 6.0. For reference, the dielectric constantmentioned herein indicates a dielectric constant at 30° C. Thehigh-boiling organic solvents capable of being used in combination inthe invention include, for example, dibutyl phthalate, dimethylphthalate, tricresyl phosphate, tributyl phosphate and the like.

The phthalate advantageously used in the invention, include, forexample, those represented by the following Formula [XII]: ##STR14##wherein, R₁₂ and R₁₃ represent an alkyl group, an alkenyl group or anaryl group, provided that an aggregate number of the the carbon atomsthereof is from 9 to 32 and, more preferably, from 16 to 24.

In the invention, the alkyl groups represented by R₁₂ or R₁₃ in theabove-given Formula [XII] are of the normal chained or branch chainedinclude, for example, a butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl and octadecyl groups. The aryl groups represented by R₁₂ orR₁₃ in the Formula include, for example, a phenyl and naphthyl groups.The alkenyl groups represented thereby include, for example, a hexenyl,heptenyl and octadecenyl groups. These alkyl, alkeyl and aryl groupseach may have a single or plural substituents. The substituents of thealkyl and alkenyl groups include, for example, a halogen, an alkoxy,aryl, aryloxy, alkenyl and alkoxycarbonyl groups. The substituents ofthe aryl groups include, for example, a halogen, an alkyl, alkoxy, aryl,aryloxy, alkenyl and alkoxycarbonyl groups. Not less than two of theabove-mentioned substituents may also be introduced into the alkyl,alkenyl or aryl groups.

The phosphate capable of being advantageously used in the inventioninclude, for example, those represented by the following Formula [XIII]:##STR15## wherein R₁₄, R₁₅ and R₁₆ represent an alkyl, alkenyl or arylgroup, respectively, provided that an aggregate number of the carbonatoms thereof is from 24 to 54.

The alkyl groups represented by R₁₄, R₁₅ and R₁₆ include, for example, abutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl andnonadecyl groups. The aryl groups represented thereby include, forexample, a phenyl and naphthyl groups. The alkenyl groups representedthereby include, for example, a hexenyl, heptenyl and octadecenylgroups, respectively.

These alkyl, alkenyl and aryl groups may have a single or pluralsubstituents. More preferably, R₁₄, R₁₅ and R₁₆ are an alkyl group suchas 2-ethylhexyl group, n-octyl group, 3,5,5-trimethylhexyl group,n-nonyl group, n-decyl group, sec-decyl group, t-octyl group and thelike.

The typical examples of the preferably organic solvents will be givenbelow: ##STR16##

An anionic, nonionic or cationic surface active agent may be used toserve as a dispersing assistant in such a process that a hydrophobiccompound is dissolved in an independent low-boiling solvent or in thesolvent in combination of the low-boiling solvent and a high-boilingsolvent and the resulting solution is dispersed mechanically or bymaking use of supersonic waves.

In the color photographic light-sensitive materials for printing userelating to the invention, there uses a color fog restrainer is used forpreventing a color contamination, sharpness deterioration and roughgraininess caused by the migration of the oxidation products orelectron-transferring agents of a developing agent, between the emulsionlayers (between the same color sensitive layers and/or the differentcolor sensitive layers).

The color fog restrainers may be provided to an emulsion layer in itselfor to an interlayer which is interposed between the adjacent layersthereto.

In the color photographic light-sensitive materials for printing userelating to the invention, the image stabilizers preferably usable forpreventing the deterioration of a dye image include, for example, thoserepresented by the following Formulas [A] to [H] and [J] to [K :##STR17## wherein R₁ represents hydrogen, an alkyl, alkenyl, aryl orheterocyclic group; R₂, R₃, R₅ and R₆ represents hydrogen, a halogen, ahydroxy, alkyl, alkenyl, aryl, alkoxy or acyamino group, respectively;and R₄ represents an alkyl, hydroxy, aryl or alkoxy group.

Further, R₁ and R₂ may close their rings to form a 5- or 6-memberedring, and when this is the case, R₄ represents a hydroxy or alkoxygroup. Still further, R₃ and R₄ may close their rings to form a5-membered hydrocarbon ring and when this is the case R₁ represents analkyl, aryl or heterocyclic ring, provided that, however, R₁ is nothydrogen and R₄ is not a hydroxy group.

In the above-given Formula [A], R₁ represents hydrogen, an alkyl,alkenyl, aryl or heterocyclic group, however, among them, the alkylgroups are the normal chained or branch chained ones including, forexample, a methyl, ethyl, propyl, n-octyl, tert-octyl, hexadecyl or thelike group. The phenyl groups represented by R₁ include, for example, anallyl, hexenyl, octenyl or the like group. Further, The aryl groupsrepresented by R₁ include, for example, a phenyl or naphthyl group.Still further, the heterocyclic groups represented by R₁ typicallyinclude, for example, a tetrahydropyranyl, pyrimidyl or the like group.Each of the above-mentioned groups may be able to have a substituent.The alkyl groups having a substituent include, for example, a benzyl orethoxymethyl group; the aryl groups having a substituent include, forexample, a methoxyphenyl, chlorophenyl or 4-hydroxy-3,5-dibutylphenylgroup, or the like groups.

In Formula [A], R₂, R₃, R₅ and R₆ represent hydrogen, a halogen, ahydroxy, alkyl, alkenyl, aryl, alkoxy or acylamino group and, amongthem, the alkyl, alkenyl and aryl groups include the same ones as thosealkyl, alkenyl and aryl groups represented by R₁. The above-mentionedhalogen include, for example, fluorine, chlorine, bromine and the like.Further, the above-mentioned alkoxy groups typically include, forexample, a methoxy or ethoxy group, or the like group. Still further,the above-mentioned acylamino groups are represented by R'CONH--,wherein R' represents an alkyl group such as a methyl, ethyl, n-propyl,n-butyl, n-octyl, tert-octyl or benzyl group, or the like groups; analkenyl group such as an aryl, octynyl or oleyl group, or the likegroups; an aryl group such as phenyl, ethoxyphenyl or nephthyl group, orthe like groups; or a heterocyclic group such as pyridyl or pyrimidylgroup.

In Formula [A], R₄ represents an alkyl, hydroxy, aryl or alkoxy groupand, among them, the alkyl and aryl groups typically include the sameones as those given for the alkyl and aryl groups represented by R₁ ;and the alkenyl groups represented by R₄ include the same ones as thosegiven in the alkoxy groups represented by R₂, R₃, R₅ and R₆,respectively.

R₃ and R₄ may close the rings by each other to form a ring together witha benzene ring. Such rings include, for example, those of chroman,coumaran or methylenedioxybenzene.

R₃ and R₄ may close the rings by each other to form a ring together witha benzene ring. Such rings include, for example, those of indan. Theserings may have such a substituent as that of an alkyl, alkoxy or arylgroup.

R₁ and R₂ or R₃ and R₄ may close the ring to form a ring, and the atomin the formed ring may be a spiro atom to produce a spiro compound, orR₂, R₄ and the like may be a cross-coupling group to form abis-substance.

The preferable phenol or phenylether compounds out of those representedby the afore-given Formula [A] are blind one compounds each having fourRO-groups in which R represents an alkyl, alkenyl, aryl or heterocyclicgroup, and the particularly preferably ones are represented by thefollowing Formula [A-1]; ##STR18## wherein R represents such as alkylgroup as a methyl, ethyl, propyl, n-octyl, tert-octyl, benzyl orhexadecyl group; such an alkenyl group as an allyl, octenyl or oleylgroup; such an aryl group as a phenyl or naphthyl group; or such aheterocyclic group as a tetrahydropyranyl or pyrimidyl group.

R₉ and R₁₀ represent hydrogen as fluorine, chlorine or bromine, such analkyl group as a methyl, ethyl, n-butyl or benzyl group; such an alkoxygroup as an alkyl, hexenyl or octenyl group; or such as alkoxy group asa methoxy, ethoxy or benzyloxy group.

And, R₁₁ represents hydrogen, such an alkyl group as a methyl, ethyl,n-butyl or benzyl group; such an alkenyl group as a 2-propenyl, hexenylor octenyl group; or such an aryl group as a phenyl, ethoxyphenyl,chlorophenyl or naphthyl group.

The compounds represented by the aforegiven formula [A] include thosedescribed in U.S. Pat. Nos. 3,935,016, 3,982,944 and 4,254,216; JapanesePatent O.P.I. Publication Nos. 21004/1980 and 145530/1979; BritishPatent Nos. 2,077,455, and 2,062,888; U.S. pat. Nos. 3,764,337,3,432,330, 3,574,627 and 3,573,050; Japanese Patent O.P.I. PublicationNos. 152225/1977, 20327/1978, 17729/1978 and 6321/1977; British PatentNo. 1,347,556; British Patent Open to Public Inspection No. 2,066,975;Japanese Patent Examined Publication Nos. 12337/1979 and 31625/1973;U.S. Pat. No. 3,700,455; and the like.

An amount of the compounds represented by the Formula [A] to be used ispreferably from 5 to 300 mol % and, more preferably, from 10 to 200 mol%, to an amount of magenta couplers to be used.

The typical examples of the compounds represented by Formula [A] will begiven below:

      Type (1)      ##STR19##       Type (2)      ##STR20##       Type (3)      ##STR21##       Type (4)      ##STR22##       Type (5)      ##STR23##       Type (6)      ##STR24##       Type (7)      ##STR25##       Type (1) Compound       No. R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5     R.sup.6       A-1  H OH C(CH.sub.3).sub.2 CH.sub.2 C(CH.sub.3).sub.3 CH.sub.3 O H     C(CH.sub.3).sub.2 CH.sub.2 C(CH.sub.3).sub.3 A-8  C.sub.8 H.sub.17     C(CH.sub.3 ).sub.2 C.sub.2 H.sub.5 H C.sub.8 H.sub.17      O C(CH.sub.3).sub.2 C.sub.2 H.sub.5 H A-14 H H OH C(CH.sub.3).sub.2     CH.sub.2 C(CH.sub.3).sub.3 H H A-16 H C(CH.sub.3).sub.2 C.sub.3 H.sub.7     H CH.sub.3 O C(CH.sub.3).sub.2 C.sub.3      H.sub.7 H                           Type (2) Compound         No.     R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8       A-2  CH.sub.3 OH CH.sub.3 CH.sub.3 CH.sub.3 OH CH.sub.3 CH.sub.3 A-10     CH.sub.3 OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 O CH.sub.3     CH.sub.3       Type (3) Compound       No. R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5     R.sup.6       A-3  CH.sub.3 CH.sub.3 H CH.sub.3 (t)C.sub.8 H.sub.17 OH A-11 CH.sub.3     CH.sub.3 H CH.sub.3 (t)C.sub.8 H.sub.17 C.sub.8 H.sub.17 O A-12 CH.sub.3     CH.sub.3 H CH.sub.3 CH.sub.3 O(CH.sub.2).sub.2 OC.sub.10 H.sub.21 A-17 H     CH.sub.3 CH.sub.3 CH.sub.3 (t)C.sub.8 H.sub.17 OH  A-18 CH.sub.3     CH.sub.3 CH.sub.3      ##STR26##      CH.sub.3 OH        Type (4) Compound   No. R.sup.1 R.sup.2       A-4 C.sub.3      H.sub.7     ##STR27##       A-9 C.sub.3 H.sub.7 CH.sub.2 O(CH.sub.2).sub.2 OC.sub.4      H.sub.9           Type (5) Compound      No. R.sup.1 R.sup.2 R.sup.3     R.sup.4 R.sup.5       A-5 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 O (t)C.sub.8      H.sub.17 OH           Type (6) Compound        No. R.sup.1 R.sup.2     R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7       A-6  H (t)C.sub.4 H.sub.9 CH.sub.3 CH.sub.3 (t)C.sub.4 H.sub.9 H     CH.sub.2 A-15 CH.sub.3 (t)C.sub.4 H.sub.9 CH.sub.3 CH.sub.3 (t)C.sub.4     H.sub.9 CH.sub.3 CH.sub.2       Type (7) Compound             No. R.sup.1 R.sup.2 R.sup.3 R.sup.4     R.sup.5 R.sup.6 R.sup.7 R.sup.8 R.sup.9 R.sup.10 R.sup.11 R.sup.12       A-13 H C.sub.3 H.sub.7 O C.sub.3 H.sub.7 O CH.sub.3 CH.sub.3 H H H     C.sub.3 H.sub.7 O C.sub.3 H.sub.7 O CH.sub.3 CH.sub.3 A-19 H CH.sub.3 O     CH.sub.3 O CH.sub.3 CH.sub.3 H H H CH.sub.3 O CH.sub.3 O CH.sub.3     CH.sub.3 A-20 CH.sub.3 C.sub.4 H.sub.9 O C.sub.4 H.sub.9 O CH.sub.3     CH.sub.3 H H CH.sub.3 C.sub.4 H.sub.9 O C.sub.4 H.sub.9 O CH.sub.3     CH.sub.3 A-21 H C.sub.2 H.sub.5 O C.sub.2 H.sub.5 O CH.sub.3 CH.sub.3 H     H H C.sub.2 H.sub.5 O C.sub.2 H.sub.5 O CH.sub.3 CH.sub.3 A-22 H     CH.sub.3 O CH.sub.3 O C.sub.2 H.sub.5 CH.sub.3 H CH.sub.3 H CH.sub.3 O     CH.sub.3 O CH.sub.3 C.sub.2 H.sub.5 A-23 H C.sub.7 H.sub.15 COO C.sub.7     H.sub.15 COO CH.sub.3 CH.sub.3 H H H C.sub.7 H.sub.15 COO C.sub.7     H.sub.15 COO CH.sub.3 CH.sub.3 A-24 H C.sub.4 H.sub.9 O C.sub.4 H.sub.9     O CH.sub.3 CH.sub.3 H H H C.sub.4 H.sub.9 O C.sub.4 H.sub.9 O CH.sub.3     CH.sub.3 A-25 H CH.sub.3 O(CH.sub.2).sub.2 O CH.sub.3 O(CH.sub.2).sub.2     O CH.sub.3 CH.sub.3 H H H CH.sub.3 O(CH.sub.2).sub.2 O CH.sub.3      O(CH.sub.2).sub.2 O CH.sub.3 CH.sub.3 A-26 H CH.sub.2 CHCH.sub.2 O     CH.sub.2 CHCH.sub.2 O CH.sub.3 CH.sub.3 H H H CH.sub.2 CHCH.sub.2 O     CH.sub. 2 CHCH.sub.2 O CH.sub.3 CH.sub.3 A-27 H C.sub.3 H.sub.7 O     C.sub.3 H.sub.7 O C.sub.6 H.sub.5 CH.sub.2 CH.sub.3 C.sub.6 H.sub.5 H H     C.sub.3 H.sub.7 O C.sub.3 H.sub.7 O C.sub.6 H.sub.5 O CH.sub.3 A-28     CH.sub.3 O C.sub.4 H.sub.9 O C.sub.4 H.sub.9 O CH.sub.3 CH.sub.3 H H     CH.sub.3 C.sub.4 H.sub.9 O C.sub.4 H.sub.9 O CH.sub.3 CH.sub.3 A-29 H     (s)C.sub.5 H.sub.11 O (s)C.sub.5 H.sub.11 O CH.sub.3 CH.sub.3 H H H     (s)C.sub.5 H.sub.11 O (s)C.sub.5 H.sub.11 O CH.sub.3 CH.sub.3 A-30 H     C.sub.4 H.sub.9 O C.sub.4 H.sub.9 O (i)C.sub.3 H.sub.7 CH.sub.3 CH.sub.3     CH.sub.3 H C.sub.4 H.sub.9 O C.sub.4 H.sub.9 O (i)C.sub.3 H.sub.7     CH.sub.3 A-31 H C.sub.18 H.sub.37 O C.sub.18 H.sub.37 O CH.sub.3     CH.sub.3 H H H C.sub.18 H.sub.37 O C.sub.18 H.sub.37 O CH.sub.3 CH.sub.3     A-32 H C.sub.6 H.sub.5 CH.sub. 2 O C.sub.6 H.sub.5 CH.sub.2 O CH.sub.3     CH.sub.3 H H H C.sub.6 H.sub.5 CH.sub.2 O C.sub.6 H.sub.5 CH.sub.2 O     CH.sub.3 CH.sub.3       A-7      ##STR28##       Formula [B]:      ##STR29##

wherein R₁ and R₄ represent hydrogen, a halogen, an alkyl, alkenyl,alkoxy, alkenyloxy, hydroxy, aryl, aryloxy, acyl, acylamino, acyloxy,sufonamide, cycloalkyl or alkoxycarbon group, R₂ represents hydrogen, analkyl, alkenyl, aryl, acyl, cycloalkyl or heterocyclic group; and R₃represents hydrogen, a halogen, an alkyl, alkenyl, aryl, aryloxy, acyl,acyloxy, sulfonamido, cycloalkyl or alkoxycarbonyl group.

The above-given groups may be substituted by the other substituents,respectively. They include, for example, an alkyl, alkenyl, alkoxy,aryl, aryloxy, hydroxy, alkoxycarbonyl, aryloxycarbonyl, acylamino,acyloxy, carbamoyl, sulfonamido, and sulfamoyl groups or the like.

Further, R₂ and R₃ may close the ring by each other to form a 5- or6-membered ring. The rings formed together with the benzene ring closedby R₂ and R₃ include, for example, a chroman ring and amethylenedioxybenzene ring.

Y represents a group of atoms necessary for forming a chroman orcouraman ring.

Such chroman or couraman ring may be substituted by a halogen, an alkyl,cycloalkyl, alkoxy, alkenyl, alkenyloxy, hydroxy, aryl or aryloxy groupor a heterocyclic ring; and may further form a spiro ring.

Among the compounds represented by Formula [B], the compoundsparticularly useful in the invention include those represented byFormulas [B-1], [B-2], [B-3], [B-4] and [B-5]. ##STR30##

In the above Formula [B-1] through [B-5] R₁, R₂, R₃ and R₄ aresynonymous with those denoted on the aforegiven Formula [B]; and R₅, R₆,R₇, R₈, R₉ and R₁₀ represent hydrogen, a halogen, an alkyl, alkoxy,hydroxy, alkenyl, alkenyloxy, aryl, aryloxy or heterocyclic group.

Further, R₅ and R₆, R₆ and R₇, R₇ and R₈, R₈ and R₉, and R₉ and R₁₀ maybe cyclized to form the respective carbon rings and the carbon rings mayalso be substituted by alkyl groups, respectively.

In the aforegiven Formulas [B-1] through [B-5], the particularly usefulcompounds are those in which R₁ and R₄ are hydrogen, an alkyl, hydroxyor cycloalkyl group and R₅, R₆, R₇, R₈, R₉ and R₁₀ are hydrogen, analkyl or cycloalkyl group, respectively.

The compounds represented by the Formula [B] represent and include thecompounds described in `Tetrahedron`, 1970, vol. 126, pp. 4743˜4751;`Journal of The Chemical Society of Japan`, 1972, No. 10, pp. 0987˜1990;`Chemical Letter`, 1972, No. 4, pp. 315˜316; and Japanese Patent O.P.I.Publication No. 139383/1980; and those compounds maybe synthesized inthe processes described therein.

The amount of compounds represented by the Formula [B] to be used ispreferably from 5 to 300 mol % and, more preferably, from 10 to 200 mol%, to the magenta couplers relating to the invention.

The typical examples of the above-mentioned compounds will be givenbelow:

    __________________________________________________________________________     ##STR31##                                                                    Compound                                                                      No.   R.sup.1                                                                           R.sup.2      R.sup.3                                                                             R.sup.4                                                                              R.sup.5                                                                          R.sup.6                                                                            R.sup.7                                                                         R.sup.8                                                                          R.sup.9   R.sup.10           __________________________________________________________________________    B-1   H   H            H     H      H  CH.sub.3                                                                           H H  CH.sub.3  CH.sub.3           B-2   H   H            CH.sub.3                                                                            H      H  CH.sub.3                                                                           H H  CH.sub.3  CH.sub.3           B-3   H   H            C.sub.12 H.sub.25                                                                   H      H  CH.sub.3                                                                           H H  CH.sub.3  CH.sub.3           B-4   H   H                                                                                           ##STR32##                                                                          H      H  CH.sub.3                                                                           H H  CH.sub.3  CH.sub.3           B-5   H   CH.sub.3     H     H      H  CH.sub.3                                                                           H H  CH.sub.3  CH.sub.3           B-9   CH.sub.3                                                                          H            CH.sub.3                                                                            H      H  H    H                                                                                ##STR33##   H                  B-10  H   CH.sub.3 CO  H     H      H  (i)C.sub.3 H.sub.7                                                                 H H  CH.sub.3  CH.sub.3           B-11  H   C.sub.3 H.sub.7                                                                            (t)C.sub.8 H.sub.17                                                                 H      H  CH.sub.3                                                                           H CH.sub.3                                                                         CH.sub.3  CH.sub.3           B-12  Br  H            Br    H      H  H    H CH.sub.3                                                                         CH.sub.3  CH.sub.3           B-13  H                                                                                  ##STR34##   H     H      CH.sub.3                                                                         CH.sub.3                                                                           H H  CH.sub.2 OH                                                                             CH.sub.3           B-14  H                                                                                  ##STR35##   H     H      CH.sub.3                                                                         CH.sub.3                                                                           H H  CH.sub.3  CH.sub.3           B-15  H   H            CH.sub.2 CHCH.sub.2 CO                                                                     CH.sub.3                                                                         CH.sub.3                                                                           H H                                                                                 ##STR36##                                                                              CH.sub.3           B-16  H   H            H     CH.sub.3 SO.sub.2 NH                                                                 CH.sub.3                                                                         CH.sub.3                                                                           H H                                                                                 ##STR37##                                                                              CH.sub.3           B-17  H                                                                                  ##STR38##   CH.sub.3                                                                            H      Cl H    Cl                                                                              H  CH.sub.3  CH.sub.3           B-18  H                                                                                  ##STR39##   CH.sub.3 CONH                                                                       H      H  H    H H                                                                                 ##STR40##                   B-54  CH.sub.3 O                                                                        CH.sub.3 O   H     H      H  H    H H  CH.sub.3  CH.sub.3           B-55  H                                                                                  ##STR41##         H      H  H    H H  CH.sub.3  CH.sub.3           __________________________________________________________________________     ##STR42##                                                                    Compound                                                                      No.   R.sup.1                                                                          R.sup.2     R.sup.3   R.sup.4                                                                             R.sup.5                                                                            R.sup.6 R.sup.7                                                                              R.sup.8              __________________________________________________________________________    B-6   H  H           H         H     H                                                                                   ##STR43##     H                    B-7   H  H           (i)C.sub.3 H.sub.7                                                                      H     H    H       CH.sub.3                                                                             CH.sub.3             B-8   H  CH.sub.3    Cl        H     H    H       CH.sub.3                                                                             CH.sub.3             B-19  H  H                                                                                          ##STR44##                                                                              H     CH.sub.3                                                                           CH.sub.3                                                                              CH.sub.3                                                                             CH.sub.3             B-20  H  CH.sub.2 CHCH.sub.2                                                                       CH.sub.3  H     CH.sub.3                                                                           CH.sub.3                                                                              CH.sub.3                                                                             H                    B-21  H  C.sub.3 H.sub.7                                                                           C.sub.3 H.sub.7                                                                         H     CH.sub.3                                                                           CH.sub.3                                                                               ##STR45##                                                                           H                    B-22  CH.sub.3                                                                         H           CH.sub.3  H                                                                                    ##STR46##   H      H                    B-23  CH.sub.3                                                                         H                                                                                          ##STR47##                                                                              H     CH.sub.3                                                                           CH.sub.3                                                                              CH.sub.3                                                                             CH.sub.3             __________________________________________________________________________     ##STR48##                                                                    Compound                                                                      No.   R.sup.1                                                                          R.sup.2       R.sup.3   R.sup.4 R.sup.5                                                                            R.sup.6  R.sup.9                                                                         R.sup.10             __________________________________________________________________________    B-24  H  H             H         H       CH.sub.3                                                                           CH.sub.3 H H                    B-25  H  H             CH.sub.3  H       CH.sub.3                                                                           CH.sub.3 H H                    B-26  H  H             (t)C.sub.4 H.sub.9                                                                      H       H    H        H H                    B-27  H  CH.sub.3      H         H       CH.sub.3                                                                           CH.sub.3 H H                    B-28  H  H                                                                                            ##STR49##                                                                              H       CH.sub.3                                                                           CH.sub.3 H H                    B-29  H  H             C.sub.2 H.sub.5 COOCH.sub.2                                                             H       CH.sub.3                                                                           CH.sub.3 H H                    B-30  CH.sub.3                                                                          ##STR50##    H         CH.sub.3                                                                              CH.sub.3                                                                           CH.sub.3 H H                    B-31  Cl H             H         H                                                                                      ##STR51##    H H                    B-32  H  H             CH.sub.3 CONH                                                                           H       CH.sub.3                                                                           CH.sub.3 H H                    B-33  CH.sub.3                                                                          ##STR52##    (t)C.sub.8 H.sub.17                                                                     H       CH.sub.3                                                                           CH.sub.3 H H                    B-34  H  H                                                                                            ##STR53##                                                                              H       CH.sub.3                                                                           CH.sub.3 H H                    __________________________________________________________________________     ##STR54##                                                                    Compound                                                                      No.   R.sup.1                                                                          R.sup.2     R.sup.3   R.sup.4  R.sup.5                                                                           R.sup.6   R.sup.7                                                                         R.sup.8               __________________________________________________________________________    B-35  H  H           H         H        CH.sub.3                                                                          CH.sub.3  H H                     B-36  H  C.sub.3 H.sub.7                                                                           H         H        CH.sub.3                                                                          CH.sub.3  H H                     B-37  H  CH.sub.3    CH.sub.3  H        CH.sub.3                                                                          CH.sub.3  H H                     B-38  H  H           (t)C.sub.4 H.sub.9                                                                      H        CH.sub.3                                                                          CH.sub.3  H H                     B-39  H  H                                                                                          ##STR55##                                                                              H        CH.sub.3                                                                          CH.sub.3  H H                     B-40  H  H           CH.sub.3 SO.sub.2 NH                                                                    H        H   H         H H                     B-41  CH.sub.3                                                                          ##STR56##  H         CH.sub.3 CH.sub.3                                                                          CH.sub.3  H H                     B-42  Cl (t)C.sub.4 H.sub.9                                                                        H         H                                                                                       ##STR57##    H H                     B-43  H  C.sub.12 H.sub.25                                                                         CH.sub.3 CONH                                                                           H        CH.sub.3                                                                          CH.sub.3  H H                     B-44  H  H           (t)C.sub.8 H.sub.17                                                                     H        CH.sub.3                                                                          CH.sub.3  H H                     B-45  H  H                                                                                          ##STR58##                                                                              H        CH.sub.3                                                                          CH.sub.3  H H                     __________________________________________________________________________     ##STR59##                                                                    Compound                                                                      No.   R.sup.1                                                                           R.sup.4     R.sup.5                                                                          R.sup.6  R.sup.7                                                                           R.sup.8   R.sup.9                                                                           R.sup.10                  __________________________________________________________________________    B-46  H   H           H  H        H   H         CH.sub.3                                                                          CH.sub.3                  B-47  OH  H           H  H        H   H         CH.sub.3                                                                          CH.sub.3                  B-48  H   H           H  H        H   H         CH.sub.3                                                                          C.sub.2 H.sub.5           B-49  H   H           H  H        H   H                                                                                        ##STR60##                    B-50  C.sub.3 H.sub.7 O                                                                 H           CH.sub.3                                                                         H        H   H         CH.sub.3                                                                          CH.sub.3                  B-51  H   H           H  H        C.sub.3 H.sub.7                                                                   H         C.sub.3 H.sub.7                                                                   H                         B-52  H   OH          H  H        H   H         CH.sub.3                                                                          CH.sub.3                  B-53  H   C.sub.3 H.sub.7 O                                                                         H  H        H   H         CH.sub.3                                                                          CH.sub.3                  __________________________________________________________________________    Formula [C]:                                                                   ##STR61##                                                                    Formula [D]:                                                                   ##STR62##                                                                    __________________________________________________________________________

wherein R₁ and R₂ represent hydrogen, a halogen, an alkyl, alkenyl,alkoxy, alkenyloxy, hydroxy, aryl, aryloxy, acyl, acylamino, acyloxy,sulfonamido or alkoxycarbonyl group.

The above-given groups may be substituted by the other substituents,respectively. They include, for example, a halogen, an alkyl, alkenyl,alkoxy, aryloxy, hydroxy, alkoxycarbonyl, aryloxycarbonyl, acylamino,carbamoyl, sulfonamido and sulfamoyl groups and the like.

Y represents a group of atoms necessary for forming a dichroman ordicoumaran ring together with a benzene ring.

Such a chroman or coumaran ring may be substituted by a halogen, analkyl, cycloalkyl, alkoxy, alkenyl, alkenyloxy, hydroxyl, aryl, aryloxyor heterocyclic group; and may also form a spiro ring.

Among the compounds represented by the Formulas [C] and [D], thoseparticularly useful in the invention include, for example, the compoundsrepresented by the following Formulas [C-1], [C-2], [D-1] and [D-2]:##STR63##

In the above-given Formulas [C-1], [C-2], [D-1] and [D-2], R₁ and R₂ aresynonymous with those denoted in the aforegiven Formulas [C] and [D];and R₃ ; R₄, R₅, R₆, R₇ and R₈ represent hydrogen, a halogen, an alkyl,alkoxy, hydroxy, alkenyl, alkenyloxy, aryl, aryloxy or heterocyclicgroup. Further, R₃ and R₄, R₄ and R₅, R₅ and R₆, R₆ and R₇ and R₇ and R₈may be cyclized each other to form a carbon ring; and still further,such a carbon ring may also be substituted by an alkyl group.

In the above-given Formulas [C-1], [C-2], [D-1] and [D-2], theparticularly useful compounds are those in which R₁ and R₂ representhydrogen, an alkyl, alkoxy, hydroxy or cycloalkyl group, and R₃, R₄, R₅,R₆, R₇ and R₈ represent hydrogen, an alkyl or cycloalkyl group.

The compounds represented by the Formulas [C] and [D] include thosedescribed in `Journal of The Chemical Society of Japan`, Part C, 1968,(14), pp. 1939˜18; `Journal of The Society of Synthesis OrganicChemistry, Japan`, 1970, 28(1), pp. 60˜65; and `Tetrahedron Letters`,1973, (29), pp. 2707˜2710; and they may be synthesized in the processesdescribed therein.

An amount of the compounds represented by the aforegiven Formulas [C] tobe used is preferably from 5 to 300 mol % and, more preferably, from 10to 200 mol %, to the magenta couplers used in the invention.

The typical examples of the above-mentioned compounds will be givenbelow:

    __________________________________________________________________________     ##STR64##                                                                    Compound                                                                      No.   R.sup.1                                                                         R.sup.2  R.sup.3                                                                         R.sup.4     R.sup.5                                                                            R.sup.6                                   __________________________________________________________________________    C-11  H H        H H           CH.sub.3                                                                           CH.sub.3                                  C-12  H H        H H                                                                                          ##STR65##                                     C-13  H H        H                                                                                ##STR66##       H                                         __________________________________________________________________________     ##STR67##                                                                    Compound                                                                      No.   R.sub.1   R.sub.2   R.sub.3                                                                          R.sub.4                                                                          R.sub.5                                                                         R.sub.6                                                                         R.sub.7                                                                            R.sub.8                              __________________________________________________________________________    C-1   H         H         H  H  H H H    H                                    C-2   H         H         H  H  H H CH.sub.3                                                                           CH.sub.3                             C-3   H         H         CH.sub.3                                                                         H  H H CH.sub.3                                                                           CH.sub.3                             C-4   CH.sub.3  H         CH.sub.3                                                                         CH.sub.3                                                                         H H CH.sub. 3                                                                          CH.sub.3                             C-5   OH        H         H  H  H H C.sub.2 H.sub.5                                                                    CH.sub.3                             C-6   OCH.sub.3 H         H  H  H H H    H                                    C-7   OC.sub.3 H.sub.7                                                                        H         H  H  H H H    H                                    C-8   OC.sub.12 H.sub.25                                                                      H         H  H  H H H    H                                    C-9   CH.sub.3 COO                                                                            H         H  H  H H CH.sub.3                                                                           CH.sub.3                             C-10  CH.sub.3 CONH                                                                           H         H  H  H H                                                                                ##STR68##                                C-14                                                                                 ##STR69##                                                                               ##STR70##                                                                              H  H  H H CH.sub.3                                                                           CH.sub.3                             C-15  CH.sub.3  CH.sub.3  H  H  H H CH.sub.3                                                                           CH.sub.3                             C-16  (CH.sub.3).sub.2 CCHCH.sub.2                                                            (CH.sub.3).sub.2 CCCH.sub.2                                                             H  H  H H CH.sub.3                                                                           CH.sub.3                             C-17  Cl        H         H  H  H H H    H                                    __________________________________________________________________________     ##STR71##                                                                    Compound                                                                      No.   R.sub.1                                                                          R.sub.2    R.sub.3                                                                         R.sub.4   R.sub.5                                                                          R.sub.6                                    __________________________________________________________________________    D-1   CH.sub.3                                                                         CH.sub.3   H H         H  H                                          D-2   H  H          H H         CH.sub.3                                                                         CH.sub.3                                   __________________________________________________________________________     ##STR72##                                                                    Compound                                                                      No.   R.sub.1  R.sub.2  R.sub.3                                                                         R.sub.4                                                                          R.sub.5                                                                         R.sub.6                                                                          R.sub.7 R.sub.8                             __________________________________________________________________________    D-3   H        H        H H  H H  H       H                                   D-4   H        H        H H  H H  CH.sub.3                                                                              CH.sub.3                            D-5   CH.sub.3 CH.sub.3 H H  H H  CH.sub.3                                                                              CH.sub.3                            D-6                                                                                  ##STR73##                                                                              ##STR74##                                                                             H H  H H  CH.sub.3                                                                              CH.sub.3                            D-7   H        H        Cl                                                                              H  Cl                                                                              H  H       H                                   D-8   H        H        H H  H H                                                                                 ##STR75##                                  D-9   CH.sub.3 O                                                                             H        H H  H H                                                                                 ##STR76##                                                                            H                                   D-10  H        H        H H  H H  CH.sub.2 OH                                                                           CH.sub.3                            D-11                                                                                 ##STR77##                                                                             H        H H  H H  CH.sub.3                                                                              CH.sub.3                            __________________________________________________________________________    Formula [E]:                                                                   ##STR78##                                                                    __________________________________________________________________________

wherein R¹ represents hydrogen, an alkyl, alkenyl, aryl, acyl,cycloalkyl or heterocyclic group; and R³ represents hydrogen, a halogen,an alkyl, alkenyl, aryl, aryloxy, acyl, acylamino, acyloxy, sulfonamido,cycloalkyl or alkoxycarbonyl group.

R² and R⁴ represent hydrogen, a halogen, an alkyl, alkenyl, aryl, acyl,acylamino, sulfonamido, cycloalkyl or alkoxycarbonyl group.

The above-mentioned groups may be substituted by the other substituents,respectively. They include, for example, an alkyl, alkenyl, alkoxy,aryl, aryloxy, hydroxy, alkoxycarbonyl, aryloxycarbonyl, acylamino,carbamoyl, sulfonamido, sulfamoyl or like group.

Further, R¹ and R² may close a ring each to form a 5- or 6-memberedring, provided that, in this case, R³ and R⁴ represent hydrogen, ahalogen, an alkyl, alkenyl, alkoxy, alkenyloxy, hydroxy, aryl, aryloxy,acyl, acyloxy, sulfonamido or alkoxycarbonyl group.

Y represents a group of atoms necessary for forming a chroman orcoumaran ring.

Such a chroman or coumaran ring may be substituted by a halogen, analkyl, cycloalkyl, alkoxy, alkenyl, alkenyloxy, hydroxy, aryl, aryloxyor heterocyclic group; and may further form a spiro ring.

Among the compounds represented by the Formula [E] include, for example,those represented by the following Formulas [E-1], [E-2], [E-3], [E-5],##STR79##

In the above-given Formulas [E-1] through [E-5], R¹, R², R³ and R⁴ aresynonymous with those denoted in the aforgiven Formula [E]; and R⁵, R⁶,R⁷, R⁸, R⁹ and R¹⁰ represent hydrogen, a halogen, an alkyl, alkoxy,hydroxy, alkenyl, alkenyloxy, aryl, aryloxy or heterocyclic group.Further, R⁵ and R⁶, R⁶ and R⁷, R⁷ and R⁸, R⁸ and R⁹, and R⁹ and R¹⁰ maybe cyclized each other to form a carbon ring; and still further, thecarbon ring may also be substituted by an alkyl group.

The compounds particularly useful include those in which R¹, R², R², R³and R⁴ represent hydrogen, an alkyl or cycloalkyl group in the Formulas[E-1] through [E-5]; R³ and R⁴ represent hydrogen, an alkyl, alkoxy,hydroxy or cycloalkyl group in the Formula [E-5]; and R⁵, R⁶, R⁷, R⁸, R⁹and R¹⁰ represent hydrogen, an alkyl or cycloalkyl group in the Formulas[E-1] through [E-5].

The compounds represented by the Formula [E] include those described in`Tetrahedron Letters`, 1965, (8), pp. 457˜460; `Journal of The ChemicalSociety of Japan`, Part C, 1966, (22), pp. 20--˜2016; and `Zh. Org.Khim.`, 1870, (6), pp. 1230˜1237; and they may be synthesized in theprocesses described therein.

An amount of the compounds represented by the Formula [E-1] to be usedis preferably from 5 to 300 mol % and more preferably from 10 to 200 mol%, to the magnet couplers relating to the invention.

The typical examples of the above-mentioned compounds will be givenbelow:

    __________________________________________________________________________     ##STR80##                                                                    Compound No                                                                           R.sub.1 R.sub.2                                                                          R.sub.3                                                                             R.sub.4                                                                          R.sub.5                                                                          R.sub.6                                                                           R.sub.7                                                                              R.sub.8                             __________________________________________________________________________    E-19    H       H  H     H  H                                                                                 ##STR81## H                                   E-20    C.sub.3 H.sub.7                                                                       H  H     H  H                                                                                 ##STR82## H                                   E-21    H       H  H     H  H  H                                                                                  ##STR83##                                 E-22    CH.sub.3                                                                              H  H     H  H  H                                                                                  ##STR84##                                                                           H                                   E-23    H       H  H     H  H  H   CH.sub.3                                                                             CH.sub.3                            E-24    CH.sub.3                                                                              H                                                                                 ##STR85##                                                                          H  H  H   CH.sub.3                                                                             CH.sub.3                            E-25                                                                                   ##STR86##                                                                            H  H     H  H  H   CH.sub.3                                                                             CH.sub.3                            E-26    C.sub.12 H.sub.25                                                                     H  H     H  CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                             CH.sub.2 OH                         __________________________________________________________________________     ##STR87##                                                                    Compound No                                                                           R.sub.1  R.sub.2                                                                         R.sub.3 R.sub.4                                                                         R.sub.5                                                                          R.sub.6                                                                           R.sub.7                                                                          R.sub.8                                                                         R.sub.9                                                                          R.sub.10                          __________________________________________________________________________    E-1     H        H H       H H  H   H  H H  H                                 E-2     H        H H       H H  H   H  H CH.sub.3                                                                         CH.sub.3                          E-3     H        H H       H CH.sub.3                                                                         H   H  H CH.sub.3                                                                         CH.sub.3                          E-4     H        H CH.sub.2 CHCH.sub.2                                                                   H H  H   H  H CH.sub.3                                                                         CH.sub.3                          E-5     CH.sub.3 H H       H H  H   H  H CH.sub.3                                                                         CH.sub.3                          E-6     C.sub.3 H.sub.7                                                                        H H       H H  H   H  H CH.sub.3                                                                         CH.sub.3                          E-7     C.sub.12 H.sub.25                                                                      H H       H CH.sub.3                                                                         H   H  H CH.sub.3                                                                         CH.sub.3                          E-8                                                                                    ##STR88##                                                                             H H       H H  H   H  H H  H                                 E-9                                                                                    ##STR89##                                                                             H H       H H  H   H  H CH.sub.3                                                                         CH.sub.3                          E-10                                                                                   ##STR90##                                                                             H H       H H  H   H  H CH.sub.3                                                                         CH.sub.3                          E-11    H        H H       H H  H   H  H CH.sub.3                                                                         C.sub.16 H.sub.33                 E-12    H        H                                                                                ##STR91##                                                                            H H  H   H  H CH.sub.3                                                                         CH.sub.3                          E-13    CH.sub.3 H CH.sub.3 CO                                                                           H H  H   H  H CH.sub.3                                                                         CH.sub.3                          E-14    CH.sub.3 H H       H H  Br  Br H H  H                                 E-15    CH.sub.3 H H       H H  Cl  Cl H H  H                                 E-16    CH.sub.3 H H       H H  CH.sub.3 O                                                                        Br H H  H                                 E-17    CH.sub.3 H H       H H  OH  Br H CH.sub.3                                                                         CH.sub.3                          E-18    CH.sub.3 H H       H H  C.sub.2 H.sub.5 O                                                                 OH H CH.sub.3                                                                         CH.sub.3                          __________________________________________________________________________     ##STR92##                                                                    Compound No                                                                           R.sub.1   R.sub.2                                                                           R.sub.3                                                                          R.sub.4 R.sub.5                                                                          R.sub.6                                                                            R.sub.9                                                                          R.sub.10                          __________________________________________________________________________    E-27    H         H   H  H       H  H    H  H                                 E-28    CH.sub.3  H   H  H       H  H    H  H                                 E-29                                                                                   ##STR93##                                                                              H   H  H       H  H    H  H                                 E-30    H         H   CH.sub.3                                                                         H       H  H    CH.sub.3                                                                         CH.sub.3                          E-31    C.sub.3 H.sub.7                                                                         H   H  H       H  H    H  H                                 E-32    C.sub.3 H.sub.7                                                                         H   H  H       CH.sub.3                                                                         CH.sub.3                                                                           H  H                                 E-37    H         H   H  CH.sub.3 CONH                                                                         H  H    H  H                                 E-38    CO        H   H  H       H  H    H  H                                 __________________________________________________________________________     ##STR94##                                                                    Compound No                                                                             R.sub.1                                                                           R.sub.2                                                                             R.sub.3                                                                          R.sub.4                                                                              R.sub.5                                                                          R.sub.6                                                                              R.sub.7                                                                         R.sub.8                             __________________________________________________________________________    E-33      H   H     H  H      H  H      H H                                   E-34      H   H     H  H      CH.sub.3                                                                         CH.sub.3                                                                             H H                                   E-35      C.sub.12 H.sub.25                                                                 H     H  H      CH.sub.3                                                                         CH.sub.3                                                                             H H                                   E-36      CH.sub.3                                                                          H     CH.sub.3                                                                         H      CH.sub.3                                                                         CH.sub.3                                                                             H H                                   __________________________________________________________________________     ##STR95##                                                                    Compound No                                                                             R.sub.3                                                                           R.sub.4                                                                             R.sub.5                                                                          R.sub.6                                                                              R.sub.7                                                                         R.sub. 8                                                                            R.sub.9                                                                          R.sub.10                             __________________________________________________________________________    E-39      H   H     H  H      H H     H  H                                    E-40      H   H     H  H      H H     CH.sub.3                                                                         CH.sub.3                             E-41      OH  H     H  H      H H     CH.sub.3                                                                         CH.sub.3                             E-42      C.sub.3 H.sub.7 O                                                                 H     CH.sub.3                                                                         CH.sub.3                                                                             H H     H  H                                    __________________________________________________________________________    Formula [F]:                                                                   ##STR96##                                                                    __________________________________________________________________________

wherein R¹ represents hydrogen, an alkyl, alkenyl, aryl, acyl,cycloalkyl or heterocyclic group; R² represents hydrogen, a halogen, analkyl, alkenyl, aryl, aryloxy, acyl, acylamino, acyloxy, sulfonamido,cycloalkyl or alkoxycarbonyl group; R³ represents hydrogen, a halogen,an alkyl, alkenyl, aryl, acyl, acylamino, sulfonamido, cycloalkyl oralkoxycarbonyl group; and R⁴ represents hydrogen, a halogen, an alkyl,alkenyl, alkoxy, alkenyloxy, hydroxy, aryl, aryloxy, acyl, acylamino,acyloxy, sulfonamido or alkoxycarbonyl group.

The above-mentioned groups may be substituted by the other substituents,respectively. The include, for example, an alkyl, alkenyl, alkoxy, aryl,aryloxy, hydroxy, alkoxycarbonyl, aryloxycarbonyl, acylamino, carbamoyl,sulfonamido, sulfamoyl or like group.

Further, R¹ and R² may close a ring with each other to form a 5- and6-membered ring, provided that, in this case, R³ and R⁴ representhydrogen, a halogen, an alkyl, alkenyl, alkoxy, alkenyloxy, hydroxy,aryl, aryloxy, acyl, acylamino, acyloxy, sulfonamido or alkoxycarbonylgroup.

Y represents a group of atoms necessary for forming a chroman orcoumaran ring.

Such a chroman or coumaran ring may be substituted by a halogen, analkyl, cycloalkyl, alkoxy, alkenyl, alkenyloxy, hydroxy, aryl, aryloxyor heterocyclic group; and may further form a spiro ring.

Among the compounds represented by the Formula [F], the compoundsparticularly preferably in the invention include those represented bythe following Formulas [F-1], [F-2], [F-3], [F-4] and [F-5]; ##STR97##

In the above-given Formulas [F-1] through [F-5], R¹, R², R³ and R⁴ aresynonymous with those denoted in the Formula [F]; and R⁵, R⁶, R⁷, R⁸, R⁹and R¹⁰ represent hydrogen, a halogen, an alkyl, alkoxy, hydroxy,alkenyl, alkenyloxy, aryl, aryloxy or heterocyclic group.

Further, R⁵ and R⁶, R⁶ and R⁷, R⁷ and R⁸, R⁸ and R⁹, and R⁹ and R¹⁰ maybe cyclized each other to form a carbon ring; and the carbon ring mayalso be substituted by an alkyl group.

Still further, in the above-given Formulas [F-3], [F-4] and [F-5], twoeach of from R¹ through R¹⁰ may be the same or different from eachother.

In the Formulas [F-1]through [F-5], the particularly preferablycompounds are those in which R¹, R² and R³ represent hydrogen, an alkylor cycloalkyl group; R⁴ represent hydrogen, an alkyl, alkoxy, hydroxy orcycloalkyl group, and R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ represent hydrogen, analkyl or cycloalkyl group.

The compounds represented by the Formula [F] include those described in`Tetrahedron Letters', 1970, vol. 26, pp. 4743˜4751; `Journal of TheChemical Society of Japan`, 1972, No. 10, pp. 1987˜1990; `Synthesis`,1975, vol. 6, pp. 392˜393; and `Bul. Soc. Chem. Belg.`, 1975, vol.84(7), pp. 747˜759; and they may be synthesized in the processesdescribed therein.

An amount of the compounds represented by the Formula [F] to be used ispreferably from 5 to 300 mol %, more preferably, from 10 to 200 mol %,to the magenta couplers relating to the invention.

The typical examples of the compounds represented by the Formula [F]will be given below:

    __________________________________________________________________________     ##STR98##                                                                    Compound No                                                                           R.sub.1 R.sub.2                                                                            R.sub.3                                                                             R.sub.4                                                                           R.sub.5                                                                          R.sub.6  R.sub.7                                                                           R.sub.8                        __________________________________________________________________________    F-11    H       H    H     H   H                                                                                 ##STR99##   H                              F-12    C.sub.3 H.sub.7                                                                       H    H     H   H                                                                                 ##STR100##  H                              F-13    H       H    H     H   H  H        H   H                              F-14    H       H    H     H   H  H        CH.sub.3                                                                          H                              F-15    H       H    CH.sub.3                                                                            H   H  H        CH.sub.3                                                                          H                              F-16    H       H                                                                                   ##STR101##                                                                         H   H  H        CH.sub.3                                                                          H                              F-17    H       H                                                                                   ##STR102##                                                                         H   H  H        CH.sub.3                                                                          H                              F-18    C.sub.3 H.sub.7                                                                       H    CH.sub.3                                                                            H   H  H        CH.sub.3                                                                          H                              F-19                                                                                   ##STR103##                                                                           H    H     H                                                                                  ##STR104## H   H                              F-24    CH.sub.2 CHCH.sub.2                                                                   CH.sub.3                                                                           CH.sub.3                                                                            H   H  C.sub.2 H.sub.5 O                                                                      CH.sub.3                                                                          CH.sub.3                       F-25    C.sub.3 H.sub.7                                                                       H    H     H   H                                                                                 ##STR105##                                                                            CH.sub.3                                                                          CH.sub.3                       F-26    H       CH.sub.3                                                                           CH.sub.3                                                                            H   H  H                                                                                       ##STR106##                        __________________________________________________________________________     ##STR107##                                                                   Compound No                                                                           R.sub.1  R.sub.2   R.sub.3                                                                         R.sub.4                                                                         R.sub.5                                                                          R.sub.6                                                                            R.sub.7                                                                            R.sub.8                                                                          R.sub.9                                                                          R.sub.10                    __________________________________________________________________________    F-1     H        H         H H H  H    H    H  H  H                           F-2     H        H         H H CH.sub.3                                                                         CH.sub.3                                                                           H    H  CH.sub.3                                                                         H                           F-3     H        H         H H CH.sub.3                                                                         CH.sub.3                                                                           H    H  H  H                           F-4     H        (CH.sub.3).sub.2 CCCHCH.sub.2                                                           H H CH.sub.3                                                                         CH.sub.3                                                                           H    H  H  H                           F-5     CH.sub.3 H         H H CH.sub.3                                                                         CH.sub.3                                                                           H    H  H  H                           F-6     C.sub.3 H.sub.7                                                                        H         H H CH.sub.3                                                                         CH.sub.3                                                                           H    H  H  H                           F-7     C.sub.12 H.sub.25                                                                      H         H H CH.sub.3                                                                         CH.sub.3                                                                           H    H  H  H                           F-8                                                                                    ##STR108##                                                                            H         H H CH.sub.3                                                                         CH.sub.3                                                                           H    H  H  H                           F-9                                                                                    ##STR109##                                                                            H         H H CH.sub. 3                                                                        CH.sub.3                                                                           H    H  H  H                           F-10                                                                                   ##STR110##                                                                            H         H H CH.sub.3                                                                         CH.sub.3                                                                           H    H  H  H                           F-20    H        Cl        H H H                                                                                 ##STR111##                                                                             H  H  H                           F-21    H        H         H H CH.sub.3                                                                         CH.sub.2 OH                                                                        H    H  CH.sub.3                                                                         CH.sub.3                    F-22    C.sub.3 H.sub.7                                                                        (t)C.sub.8 H.sub.17                                                                     H H C.sub.2 H.sub.5                                                                  CH.sub.3                                                                           H    H  H  H                           F-23    CH.sub.3 CO                                                                            H         H H CH.sub.3                                                                         CH.sub.3                                                                           H    H  CH.sub.3                                                                         H                           __________________________________________________________________________     ##STR112##                                                                   Compound No                                                                             R.sub.1  R.sub.2                                                                            R.sub.3                                                                         R.sub.4 R.sub.5                                                                         R.sub.6                                                                            R.sub.9                                                                           R.sub.10                         __________________________________________________________________________    F-27      H        H    H H       H H    CH.sub.3                                                                          CH.sub.3                         F-28      C.sub.3 H.sub.7                                                                        H    H H       H H    CH.sub.3                                                                          CH.sub.3                         F-29      H        H    H (t)C.sub.8 H.sub.17                                                                   H H    H   H                                F-30      H        Cl   H H       H H                                                                                   ##STR113##                          F-31                                                                                     ##STR114##                                                                            H    H H       H H    CH.sub.3                                                                          CH.sub.3                         __________________________________________________________________________     ##STR115##                                                                   Compound No                                                                           R.sub.1  R.sub.2   R.sub.3                                                                             R.sub.4                                                                              R.sub.7                                                                         R.sub.8                                                                         R.sub.9                                                                           R.sub.10                      __________________________________________________________________________    F-32    H        H         H     H      H H CH.sub.3                                                                          CH.sub.3                      F-33    CH.sub.3 H         H     H      H H CH.sub.3                                                                          CH.sub.3                      F-34    H        CH.sub.3  H     H      H H H   H                             F-35    H        H         H     (t)C.sub.4 H.sub.9                                                                   H H CH.sub.3                                                                          CH.sub.3                      F-36    H                                                                                       ##STR116##                                                                             H     H      H H CH.sub.3                                                                          CH.sub.3                      F-37    H        H         H     CH.sub.3 SO.sub.2 NH                                                                 H H H   H                             F-38                                                                                   ##STR117##                                                                            H         H     H      H H CH.sub.3                                                                          CH.sub.3                      F-39    C.sub.12 H.sub.25                                                                      H         H     H      H H CH.sub.3                                                                          CH.sub.3                      F-40                                                                                   ##STR118##                                                                            H         H     H      H H                                                                                ##STR119##                       F-41    H        H                                                                                        ##STR120##                                                                         H      H H CH.sub.3                                                                          CH.sub.3                      __________________________________________________________________________     ##STR121##                                                                    Compound No                                                                            R.sub.3                                                                           R.sub.4 R.sub.5                                                                           R.sub.6 R.sub.7                                                                         R.sub.8                                                                            R.sub.9                                                                          R.sub.10                          __________________________________________________________________________    F-42      H   H       CH.sub.3                                                                          CH.sub.3                                                                              H H    H  H                                 F-43      H   H                                                                                      ##STR122## H H    H  H                                 F-44      H   OH      CH.sub.3                                                                          CH.sub.3                                                                              H H    CH.sub.3                                                                         H                                 F-45      H   C.sub.3 H.sub.7 O                                                                     H   H       H H    CH.sub.3                                                                         CH.sub.2 OH                       F-46      OH  H       CH.sub.3                                                                          CH.sub.3                                                                              H H    H  H                                 F-47      C.sub.3 H.sub.7 O                                                                 H       CH.sub.3                                                                          CH.sub.3                                                                              H H    H  H                                 __________________________________________________________________________    Formula [G]:                                                                   ##STR123##                                                                   __________________________________________________________________________

wherein R¹ and R³ represent hydrogen, a halogen, an alkyl, alkenyl,alkoxy, hydroxy, aryl, aryloxy, acyl, acylamino, acyloxy, sulfonamido,cycloalkyl or alkoxycarbonyl group; and R² represents hydrogen, ahalogen, an alkyl, alkenyl, hydroxyl, aryl, acyl, acylamino, acyloxy,sulfonamido, cycloalkyl or alkoxycarbonyl group.

The above-mentioned groups may be substituted by the other substituentsincluding, for example, an alkyl, alkenyl, alkoxy, aryl, aryloxy,hydroxy, alkoxycarbonyl, aryloxycarbonyl, acylamino, carbamoyl,sulfonamido, sulfamoyl or like group.

R² and R³ may close a ring with each other to form a 5- or 6-memberedhydrocarbon ring which may also be substituted by a halogen, an alkylcycloalkyl, alkoxy, alkenyl, hydroxy, aryl, aryloxy, heterocyclic orlike group.

Y represents a group of atoms necessary for forming an indan ring whichmay also be substituted by a halogen, an alkyl, alkenyl, alkoxycyclokalkyl, hydroxy, aryl, aryloxy, heterocyclic or like group; and mayfurther form a spiro ring.

Among the compounds represented by the Formula [G], those particularlypreferred include the compounds represented by the following Formulas[G-1] through [G-3]: ##STR124##

In the above-given Formulas [G-1] through [G-3], R¹, R² and R³ aresynonymous with those denoted in the Formula [G]; and R⁴, R⁵, R⁶, R⁷, R⁸and R⁹ represent hydrogen, a halogen, an alkyl, alkoxy, alkenyl,hydroxy, aryl, aryloxy or heterocyclic group.

R⁴ and R⁵, R⁵ and R⁶, R⁶ and R⁷, R⁷ and R⁸, and R⁸ and R⁹ may close aring with each other to form a hydrocarbon ring which may further besubstituted by an alkyl group.

In the above-given Formulas [G-1] through [G-3], the particularly usefulcompounds are those in which R¹ and R³ represent hydrogen, an alkyl,alkoxy, hydroxy or cycloalkyl group; R² represent hydrogen, an alkyl,hydroxy or cycloalkyl group; and R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ representhydrogen, an alkyl or cycloalkyl group.

An amount of the compounds represented by the above-given Formula [G] tobe used is preferably from 5 to 300 mol % and, more preferably, from 10to 200 mol %, to the magenta couplers.

The typical examples of the compounds represented by the Formula [G]will be given below:

    __________________________________________________________________________     ##STR125##                                                                   Compound                                                                      No.   R.sup.1                                                                           R.sup.2   R.sup.3                                                                            R.sup.4                                                                             R.sup.5                                                                             R.sup.6                                                                           R.sup.7                                                                         R.sup.8                                                                           R.sup.9                        __________________________________________________________________________    G-1   H   H         H    H     H     H   H H   H                              G-2   H   H         H    H     H     H   H CH.sub.3                                                                          CH.sub.3                       G-3   H   H         H    H     H     H   H CH.sub.3                                                                          C.sub.16 H.sub.33              G-4   H   OH        H    H     H     H   H CH.sub.3                                                                          C.sub.16 H.sub.33              G-5   H   H         H    CH.sub.3                                                                            CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                       G-6   H   Cl        H    CH.sub.3                                                                            CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                       G-7   Cl  Cl        H    CH.sub.3                                                                            CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                       G-8   H   H         CH.sub.3                                                                           CH.sub.3                                                                            CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                       G-9   H   H         H    H                                                                                    ##STR126##                                                                             H H   H                              G-10  H   H         H    H     H     H   H                                                                                ##STR127##                        G-11  H   C.sub.3 H.sub.7                                                                         H    CH.sub.3                                                                            CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                       G-12  H   (t)C.sub.8 H.sub.17                                                                     H    CH.sub.3                                                                            CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                       G-13  H                                                                                  ##STR128##                                                                             H    CH.sub.3                                                                            CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                       G-14  H   H         H                                                                                   ##STR129##                                                                         CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                       G-15  H   H         CH.sub.3 O                                                                         CH.sub.3                                                                            CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                       G-16  CH.sub.3 H                                                                        H         H    H                                                                                    ##STR130##                                                                             H H   H                              G-17  H   CH.sub.3 SO.sub.2 NH                                                                    H    CH.sub.3                                                                            CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                       G-18  H   CH.sub.3 CO                                                                             H    CH.sub.3                                                                            CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                       G-19  H                                                                                  ##STR131##                                                                             H    CH.sub.3                                                                            CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                       G-20  H                                                                                  ##STR132##                                                                             H    CH.sub.3                                                                            CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                       G-21  H                                                                                  ##STR133##    H     H     H   H H   H                              G-22  H                                                                                  ##STR134##    CH.sub.3                                                                            CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                       G-23  H                                                                                  ##STR135##    CH.sub.3                                                                            CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                       G-24  CH.sub.3                                                                           ##STR136##    CH.sub.3                                                                            CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                       __________________________________________________________________________     ##STR137##                                                                   Compound                                                                      No.   R.sup.1   R.sup.2                                                                         R.sup.3  R.sup.6                                                                         R.sup.7  R.sup.8                                                                          R.sup.9                              __________________________________________________________________________    G-29  H         H H        H H        CH.sub.3                                                                         CH.sub.3                             G-32  CH.sub.3  H H        H H        CH.sub.3                                                                         CH.sub.3                             __________________________________________________________________________     ##STR138##                                                                   Compound                                                                      No.   R.sub.1  R.sub.2   R.sub.3                                                                             R.sub.4                                                                           R.sub.5  R.sub.6                                                                          R.sub.7                        __________________________________________________________________________    G-25  H        CH.sub.3  H     CH.sub.3                                                                          C.sub.6 H.sub.5                                                                        H  H                              G-26  Cl       Cl        H     CH.sub.3                                                                          CH.sub.3 H  H                              G-27  H        OH        H     CH.sub.3                                                                          CH.sub.3 H  H                              G-28  H        C.sub.3 H.sub.7                                                                         H     CH.sub.3                                                                          CH.sub.3 H  H                              G-30  H        Cl        H     CH.sub.3                                                                          CH.sub.3 H  H                              G-31  H        C.sub.2 H.sub.5                                                                         H     CH.sub.3                                                                          CH.sub.3 H  H                              G-33  CH.sub.3 CH.sub.3  H     CH.sub.3                                                                          CH.sub.3 H  H                              G-34  H                                                                                       ##STR139##                                                                             H     CH.sub.3                                                                          CH.sub.3 H  H                              G-35  H        CH.sub.3  H     H   H        H  H                              G-36  H        H         H                                                                                    ##STR140##  H  H                              G-37  CH.sub.3 H         H     CH.sub.3                                                                          CH.sub.3 H  H                              G-38  H        CH.sub.3  H     CH.sub.3                                                                          C.sub.6 H.sub.5                                                                        H  H                              G-39                                                                                 ##STR141##                                                                            H         H     CH.sub.3                                                                          CH.sub.3 H  H                              G-40  CH.sub.3 CH.sub.3  H     C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                        H  H                              G-41  H        H         H     H   H        CH.sub.3                                                                         CH.sub.3                       G-42  H        OH        H                                                                                    ##STR142##  H  H                              G-43  H                                                                                       ##STR143##                                                                             H     H   H        H  H                              G-44  H        (t)C.sub.4 H.sub.9                                                                      H     CH.sub.3                                                                          CH.sub.3 H  H                              G-45  H        (t)C.sub.8 H.sub.17                                                                     H     CH.sub.3                                                                          CH.sub.3 H  H                              __________________________________________________________________________    Formula [H]:                                                                   ##STR144##                                                                   __________________________________________________________________________

wherein R¹ and R² represents hydrogen, a halogen, an alkyl, alkenyl,aryl, acyl, acylamino, acyloxy, sulfonamido, cycloalkyl oralkoxycarbonyl group, respectively;

R³ represents hydrogen, a halogen, an alkyl, alkenyl, alkoxy, hydroxy,aryl, aryloxy, arcyl, acylamino, acyloxy, sulfonamido, cycloalkyl oralkoxycarbonyl group;

The above-mentioned groups may be substituted by the other substituentsincluding, for example, an alkyl, alkenyl, alkoxy, aryl, aryloxy,hydroxy, alkoxycarbonyl, aryloxycarbonyl, acylamino, carbamoyl,sulfonamido, sulfamoyl or like group;

Further, R¹ and R², and R² and R³ may close a ring with each other toform a 5- or 6-membered hydrocarbon ring which may further besubstituted by a halogen, an alkyl, cycloalkyl, alkoxy, alkenyl,hydroxy, aryl, aryloxy, heterocyclic or like group; and

Y represents a group of atoms necessary for forming an indan ring whichmay also be substituted by a substituent capable of substituting theabove-mentioned hydrocarbon ring; and may further form a spiro ring.

Among the compounds represented by the above-give Formula [H], thecompounds particularly useful in the invention include those representedby the following Formulas [H-1] and [H-2]: ##STR145##

In the above-given Formulas [H-1] through [H-3], R¹, R² and R³ aresynonymous with those denoted in the Formula [H]; R⁴, R⁵, R⁶, R⁷, R⁸ andR⁹ represent hydrogen, a halogen, an alkyl, alkoxy, hydroxy, alkenyl,aryl, aryloxy or heterocyclic group; and, R⁴ and R⁵, R⁵ and R⁶, R⁶ andR⁷, R⁷ and R⁸, and R⁸ and R⁹ may close a ring with each other to form ahydrocarbon ring which may further be substituted by an alkyl group.

In the above-given Formulas [H-1] through [H-3], the particularlypreferable compounds are those in which R¹ and R² represent hydrogen, analkyl or cycloalkyl group; R³ represent hydrogen, an alkyl, alkoxy,hydroxy or cycloalkyl group; and R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ representhydrogen, an alkyl or cycloalkyl group.

The synthesizing processes of the compounds represented by the Formula[H] are already known. The compounds represented thereby may be preparedin accordance with the processes described in U.S. Pat. No. 3,057,929;`Chem Ber.`, 1972, 95(5), pp. 1673˜1674; and `Chemistry Letters`, 1980,pp. 739˜742.

The compounds represented by the Formula [H] are used in an amount ofpreferably from 5 to 300 mol % and more preferably from 10 to 200 mol %,to the magenta couplers used.

The typical examples of the compounds represented by the Formula [H]will be given below:

    __________________________________________________________________________     ##STR146##                                                                   Compound                                                                      No.   R.sup.1 R.sup.2  R.sup.3                                                                           R.sup.4                                                                          R.sup.5                                                                             R.sup.6                                                                           R.sup.7                                                                         R.sup.8                                                                           R.sup.9                         __________________________________________________________________________    H-1   H       H        H   H  H     H   H H   H                                .sup. 2                                                                            CH.sub.3                                                                              H        H   H  H     H   H H   H                                .sup. 3                                                                            H       H        H   H  H     H   H CH.sub.3                                                                          C.sub.16 H.sub.33                .sup. 4                                                                            H       H        OH  H  H     H   H H   H                                .sup. 5                                                                            CH.sub.2 CHCH.sub.2                                                                   H        Cl  H  H     H   H H   H                                .sup. 6                                                                            H       H        H   H  H     H   H CH.sub.3                                                                          CH.sub.3                          .sup. 7                                                                           H       H        H   CH.sub.3                                                                         CH.sub.3                                                                            H   H H   H                                .sup. 8                                                                            H       H        H   CH.sub.3                                                                         CH.sub.3                                                                            CH.sub.3                                                                          H H   H                                .sup. 9                                                                            CH.sub.2 CHCH.sub.2                                                                   H        CH.sub.3 O                                                                        H  H     H   H H   H                                .sup. 10                                                                           H       H        H   CH.sub.3                                                                         CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                         .sup. 11                                                                           H       C.sub.3 H.sub.7                                                                        H   CH.sub.3                                                                         CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                         .sup. 12                                                                           Cl      H        Cl  H  H     H   H CH.sub.3                                                                          CH.sub.3                        __________________________________________________________________________    Compound                                                                      No.   R.sub.1 R.sub.2  R.sub.3                                                                           R.sub.4                                                                          R.sub.5                                                                             R.sub.6                                                                           R.sub.7                                                                         R.sub.8                                                                           R.sub.9                         __________________________________________________________________________    H-13  H       H        H   H                                                                                 ##STR147##                                                                             H H   H                                .sup. 14                                                                           H       H        H   H  H     H   H                                                                                ##STR148##                          .sup. 15                                                                           H                                                                                      ##STR149##                                                                            H   CH.sub.3                                                                         CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                         .sup. 16                                                                           H       CH.sub.3 SO.sub.2 NH                                                                   H   CH.sub.3                                                                         CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                         .sup. 17                                                                           H       CH.sub.3 CO                                                                            H   H  H     H   H CH.sub.3                                                                          CH.sub.3                         .sup. 18                                                                           H                                                                                      ##STR150##                                                                            H   CH.sub.3                                                                         CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                         .sup. 19                                                                           H                                                                                      ##STR151##                                                                            H   CH.sub.3                                                                         CH.sub.3                                                                            H   H CH.sub.3                                                                          CH.sub.3                         .sup. 21                                                                            ##STR152##      CH.sub.3                                                                          H  H     H   H CH.sub.3                                                                          CH.sub.3                         .sup. 22                                                                           H       H        H   CH.sub.3                                                                          ##STR153##                                                                         H   H CH.sub.3                                                                          CH.sub.3                        __________________________________________________________________________     ##STR154##                                                                   Compound                                                                      No.   R.sub.1                                                                             R.sub.2                                                                         R.sub.3      R.sub.6                                                                         R.sub.7                                                                             R.sub.8                                                                          R.sub.9                                 __________________________________________________________________________    H-23  H     H H            H H     H  H                                        .sup. 24                                                                           H     H OH           H H     H  H                                        .sup.  25                                                                          CH.sub.3                                                                            H CH.sub.3     H H     H  H                                        .sup. 26                                                                           H     H CH.sub.3     H H     H  H                                        .sup. 27                                                                           Cl    H Cl           H H     CH.sub.3                                                                         CH.sub.3                                 .sup. 28                                                                           H     H H            H H     H                                                                                 ##STR155##                              .sup. 29                                                                           H     H H            H H     CH.sub.3                                                                          ##STR156##                              .sup. 30                                                                           H     H                                                                                ##STR157##  H H     H  H                                        .sup. 31                                                                           H     H                                                                                ##STR158##  H H     CH.sub.3                                                                         CH.sub.3                                 .sup. 36                                                                           H     H (t)C.sub.4 H.sub.9                                                                         H H     CH.sub.3                                                                         CH.sub.3                                __________________________________________________________________________     ##STR159##                                                                   Compound                                                                      No.   R.sub.1  R.sub.2                                                                         R.sub.3    R.sub.4                                                                          R.sub.5  R.sub.6                                                                         R.sub.7                             __________________________________________________________________________    H-32  H        H H          H  H        H H                                    .sup. 33                                                                           H        H H          CH.sub.3                                                                         CH.sub.3 H H                                    .sup. 34                                                                           H        H (t)C.sub.4 H.sub.9                                                                       CH.sub.3                                                                         CH.sub.3 H H                                    .sup. 35                                                                           H        H (t)C.sub.8 H.sub.17                                                                      CH.sub.3                                                                         CH.sub.3 H H                                   __________________________________________________________________________    Others:                                                                       H-20                                                                           ##STR160##                                                                   Formula [J]:                                                                   ##STR161##                                                                   __________________________________________________________________________

wherein R¹ represents an aliphatic group, a cycloalkyl group or an arylgroup; and Y represents a group of non-metal atoms necessary for forminga 5-, 6- or 7-membered heterocyclic ring together with nitrogen;provided that, when there are two or more hetero atoms in a non-metalatom containing nitrogen atom forming the heterocyclic ring, at leasttwo hetero atoms are not adjacent to each other.

The aliphatic groups represented by R¹ include, for example, a saturatedalkyl group which may have a substituent, and an unsaturated alkyl groupwhich may have a substituent. Such saturated alkyl groups include, forexample, a methyl, ethyl, butyl, octyl, dodecyl, tetracyl, hexadecyl orlike group; and such unsaturated alkyl groups include, for example, anethenyl, propenyl or like group.

The cycloalkyl groups represented by R¹ are 5-, 6- or 7-memberedcycloalkyl groups including, for example, a cyclopentyl, cyclohexyl orlike group.

The aryl groups represented by R¹ include, for example, a phenyl groupand a naphthyl group which are allowed to have a substituent.

The substituents of the aliphatic, cycloalkyl or aryl group representedby R¹ include, for example, an alkyl, aryl, alkoxy, carbonyl, carbamoyl,acylamino, sulfamoyl, sulfonamido, carbonyloxy, alkylsulfonyl,arylsulfonyl, hydroxy, heterocyclic, alkylthio, arylthio or like group;and each of these substituents may have a further substituent.

In the above-given Formula [J], Y represents a group of non-metal atomsnecessary for forming a 5-, 6- or 7-membered heterocyclic ring togetherwith nitrogen, however, at least two of the non-metal atom groups eachcontaining nitrogen forming the heterocyclic ring are to be hereto atomsand, at the same time, the two hetero atoms are not to be adjacent toeach other. In the heterocyclic ring of the compounds represented by theFormula [J], it is undesirable that all the hetero atoms are adjacent toeach other, because it is unable to display the function of a magentadye image stabilizer.

The 5-, 6- or 7-membered heterocyclic rings of the compounds representedby the Formula [J] are allowed to have such a substituent as an alkyl,aryl, acyl, carbamoyl, alkoxycarbonyl, sulfonyl or sulfamoyl group whichmay have a further substituent. In addition to the above, the 5- , 6- or7-membered heterocyclic ring may also be saturated and a saturatedheterocyclic ring is desired. It is further allowed that a benzene ringor the like may be condensed together with the heterocyclic ring or aspiro ring may be formed.

The compounds represented by the Formula [J] relating to the inventionare to be used in an amount of preferably from 5 to 300 mol % and, morepreferably, from 10 to 200 mol %, to the amount of the magenta couplersused.

The typical examples of the compounds represented by the Formula [J]will be given below:

    __________________________________________________________________________     ##STR162##                                                                      R.sup.2         R.sup.3         R.sup.4                                                                           R.sup.5                                                                          R.sup.6                                                                          R.sup.7                                                                           R.sup.8                                                                          R.sup.9                                                                           R.sup.10                                                                         R.sup.11           __________________________________________________________________________    J-1                                                                              C.sub.12 H.sub.25                                                                             C.sub.12 H.sub.25                                                                             H   H  H  H   H  H   H  H                  J-2                                                                              C.sub.14 H.sub.29                                                                             C.sub.14 H.sub.29                                                                             H   H  H  H   H  H   H  H                  J-3                                                                              C.sub.14 H.sub.29                                                                             H               H   H  H  H   H  H   H  H                  J-4                                                                              C.sub.14 H.sub.29                                                                             CH.sub.3 CO     H   H  H  H   H  H   H  H                  J-5                                                                              C.sub.16 H.sub.33                                                                             C.sub.16 H.sub.33                                                                             H   H  H  H   H  H   H  H                  J-6                                                                              C.sub.14 H.sub.29                                                                             CH.sub.3        H   H  H  H   H  H   H  H                  J-7                                                                               ##STR163##                                                                                    ##STR164##     H   H  H  H   H  H   H  H                  J-8                                                                               ##STR165##                                                                                    ##STR166##     H   H  H  H   H  H   H  H                  J-11                                                                              ##STR167##                     H   H  H  H   H  H   H  H                  J-13                                                                             C.sub.14 H.sub.29                                                                             C.sub.4 H.sub.9 NHCO                                                                          H   H  H  H   H  H   H  H                  J-14                                                                             (t)C.sub.8 H.sub.17                                                                            ##STR168##     H   H  H  H   H  H   H  H                  J-15                                                                             C.sub.14 H.sub.29                                                                             CF.sub.3 CO     H   H  H  H   H  H   H  H                  J-16                                                                             C.sub.14 H.sub.29                                                                             C.sub.2 H.sub.5 OCO                                                                           H   H  H  H   H  H   H  H                  J-17                                                                              ##STR169##                     H   H  H  H   H  H   H  H                  J-18                                                                             C.sub.14 H.sub.29                                                                             C.sub.14 H.sub.29                                                                             CH.sub.3                                                                          H  H  H   H  H   H  H                  J-19                                                                             C.sub.14 H.sub.29                                                                             C.sub.14 H.sub.29                                                                             CH.sub.3                                                                          H  H  H   H  H   CH.sub.3                                                                         H                  J-20                                                                             C.sub.14 H.sub.29                                                                             C.sub.14 H.sub.29                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3           J-21                                                                              ##STR170##                     H   H  H  H   H  H   H  H                  J-22                                                                             C.sub.12 H.sub.25                                                                             CH.sub.3        CH.sub.3                                                                          H  H  H   CH.sub.3                                                                         H   H  H                  J-23                                                                             C.sub.12 H.sub.25                                                                             C.sub.12 H.sub.25                                                                             CH.sub.3                                                                          H  H  H   H  H   CH.sub.3                                                                         H                  J-24                                                                             C.sub.16 H.sub.33                                                                             C.sub.16 H.sub.33                                                                             CH.sub.3                                                                          H  H  H   H  H   CH.sub.3                                                                         H                  J-25                                                                             C.sub.6 H.sub.5 CHCHCH.sub.2                                                                  C.sub.12 H.sub.25                                                                             H   H  H  H   H  H   H  H                  J-26                                                                             C.sub.12 H.sub.25                                                                             C.sub.2 H.sub.5 CH.sub.3                                                                          H  H  H   H  H   H  H                  J-27                                                                             C.sub.16 H.sub.33                                                                             H               C.sub.2 H.sub.5                                                                   H  H  H   H  H   H  H                  J-29                                                                             C.sub.14 H.sub.29                                                                             CH.sub.2 BrCH.sub.2                                                                           H   H  H  H   H  H   H  H                  J-30                                                                             CH.sub.3 O(CH.sub.2).sub.4                                                                    CH.sub.3 O(CH.sub.2).sub.4                                                                    H   H  H  H   H  H   H  H                  __________________________________________________________________________     ##STR171##                                                                      R.sup.2                 R.sup.3     R.sup.4                                __________________________________________________________________________    J-9                                                                              C.sub.14 H.sub.29       (CH.sub.2).sub.2                                                                          C.sub.14 H.sub.29                      J-10                                                                             (t)C.sub.8 H.sub.17     (CH.sub.2).sub.6                                                                          (t)C.sub.8 H.sub.17                    J-12                                                                             C.sub.14 H.sub.29       CH.sub.2    C.sub.14 H.sub.29                      J-28                                                                             C.sub.12 H.sub.25                                                                                      ##STR172## C.sub.12 H.sub.25                      __________________________________________________________________________     ##STR173##                                                                              X R.sub.1                                                          __________________________________________________________________________    J-31       O C.sub.12 H.sub.25                                                J-32       O C.sub.14 H.sub.29                                                J-33       O C.sub.6 H.sub.5 CHCH                                             J-34       O                                                                                ##STR174##                                                      J-35       O α-naphthyl                                                 J-36       O                                                                                ##STR175##                                                      J-37       O                                                                                ##STR176##                                                      J-38       O                                                                                ##STR177##                                                      J-39       O                                                                                ##STR178##                                                      J-40       O                                                                                ##STR179##                                                      J-41       S C.sub.14 H.sub.29                                                J-42       S                                                                                ##STR180##                                                      J-43       S                                                                                ##STR181##                                                      J-44       S                                                                                ##STR182##                                                      J-45       S                                                                                ##STR183##                                                      __________________________________________________________________________     ##STR184##                                                                              R.sup.1                                                                             R.sup.2                                                      __________________________________________________________________________    J-46       C.sub.12 H.sub.25                                                                   C.sub.12 H.sub.25                                            J-47       C.sub.14 H.sub.29                                                                   C.sub.14 H.sub.29                                            J-48       C.sub.6 H.sub.5 CH.sub.2                                                            C.sub.6 H.sub.5 CH.sub.2                                     J-49       C.sub.16 H.sub.33                                                                   H                                                            J-50       C.sub.16 H.sub.33                                                                   CH.sub.3 CO                                                              ##STR185##                                                        J-51       C.sub.16 H.sub.33                                                                   C.sub.16 H.sub.33                                            J-52       C.sub.14 H.sub.29                                                                   C.sub.14 H.sub.29                                            J-53       C.sub.12 H.sub.25                                                                   C.sub.12 H.sub.25                                            J-54       C.sub.14 H.sub.29                                                                   CH.sub.3 CO                                                  J-55       C.sub.14 H.sub.29                                                                   CF.sub.3 CO                                                  J-56       C.sub.2 H.sub.5                                                                      ##STR186##                                                  J-57       C.sub.14 H.sub.29                                                                   C.sub. 2 H.sub.5 OCO                                         J-58       C.sub.14 H.sub.29                                                                   CH.sub.3 NHCO                                                J-59       C.sub.14 H.sub.29                                                                   C.sub.4 H.sub.9 SO.sub.2                                     J-60       C.sub.14 H.sub.29                                                                   (CH.sub.3).sub.2 NSO.sub.2                                   J-61       C.sub.12 H.sub.25                                                                    ##STR187##                                                  J-62       H                                                                                    ##STR188##                                                  J-63                                                                                      ##STR189##                                                        J-64                                                                                      ##STR190##                                                        J-65                                                                                      ##STR191##                                                        J-66                                                                                      ##STR192##                                                        J-67                                                                                      ##STR193##                                                        J-68                                                                                      ##STR194##                                                        J-69                                                                                      ##STR195##                                                        J-70                                                                                      ##STR196##                                                        J-71                                                                                      ##STR197##                                                        J-72                                                                                      ##STR198##                                                        J-73                                                                                      ##STR199##                                                        J-74                                                                                      ##STR200##                                                        __________________________________________________________________________

Among the compounds represented by the Formula [J], the piperazinecompounds and the homopiperazine compounds are particularly preferred,and the compounds represented by the following Formula [J-1] or [J-2]are further particularly preferred to use; ##STR201##

In the above-given Formulas [J-1] and [J-2], R² and R³ representhydrogen, an alkyl or aryl group, provided that R² and R³ are nothydrogen at the same time; and R⁴ through R¹³ represent hydrogen, analkyl or aryl group, respectively.

In the Formulas [J-1] and [J-2], R² and R³ represent hydrogen, an alkylor aryl group. The alkyl groups represented thereby include, forexample, a methyl, ethyl, butyl, octyl, dodecyl, tetradecyl, hexadecyl,octadecyl or like group. The aryl groups represented thereby include,for example, a phenyl or like group. The alkyl groups and the arylgroups represented thereby may have substituents including, for example,a halogen, an alkyl, aryl, alkoxy, aryloxy and heterocyclic groups andthe like.

A total number of the carbon atoms of R² and R³ including thesubstituents thereof is preferably from 6 to 40.

In the above-given Formula [J-1] or [J-2], R⁴ through R¹³ representhydrogen, an alkyl or aryl group. The alkyl groups represented therebyinclude, for example, a methyl, ethyl or like group, and the aryl groupsrepresented thereby include, for example, a phenyl or like group.

The typical examples of the compounds represented by the Formula [J-1]or [J-2] are the same as those given in the exemplified piperazinecompounds [J-1] through [J-30] and the exemplified homopiperazinecompounds [J-51] through [J-62].

Next, the synthesis examples of the magenta dye image stabilizersrepresented by the aforegiven Formula [J], which are typically used inthe invention, will be given below.

SYNTHESIS EXAMPLE-1 (SYNTHESIS OF COMPOUND J-2)

Nine (9) grams of piperazine and 55 g of myristyl bromide were dissolvedin 100 ml of acetone and 15 g of anhydrous potassium carbonate were thenadded thereto. The resulted matter was boiled and refluxed for 10 hoursso as to undergo a reaction. After the reaction, the resulted reactantsolution was poured in to 500 ml of water and an extraction was thentried with 500 ml of ethyl acetate. After the resulted ethyl acetatelayer was dried with magnesium sulfate, the ethyl acetate was distilledoff. Then, the white crystallized objective matter was obtained. Therecrystallization thereof was made with 300 ml of acetone and, then, 34g of white-flaky crystals were obtained (yield: 70%).

Melting point: 55° to 58° C.

SYNTHESIS EXAMPLE-2 (SYNTHESIS OF COMPOUND J-34)

Eighteen (18) grams of 4-morpholinaniline were dissolved in 100 ml ofethyl acetate and 12 ml of acetic anhydride were added thereto little bylittle while stirring and keeping the reactant solution at 20° C. Afterthen, the resulted solution was ice-cooled and the resultantly depositedcrystals were filtered. The filtrated crystals were recrystallized withethyl acetate and, then, 16.5 g of white powder-like crystals wereobtained (yield: 75%).

Melting point: 207° to 210° C. ##STR202## wherein R¹ represents analiphatic, cycloalkyl or aryl group; Y represents a simple link ordivalent hydrocarbon group which is necessary to form a 5- to 7-memberedheterocyclic ring together with nitrogen; and R², R³, R⁴, R⁵, R⁶ and R⁷represent hydrogen, an aliphatic, cycloalkyl or aryl group, providedthat R² and R⁴, and R³ and R⁶ may couple to each other to form a simplelink so that an unsaturated 5- to 7-membered heterocyclic ring may beformed together with nitrogen and Y and, when Y is a simple link, R⁵ andR⁷ may couple to each other to form a simple link so that an unsaturated5-membered heterocyclic ring may be formed together with nitrogen and Yand further, when Y is not a simple link, R⁵ and Y, R⁷ and Y, or Yitself may form an unsaturated link so that an unsaturated 6- or7-membered heterocyclic ring together with nitrogen and Y.

The aliphatic groups represented by R¹ include, for example, a saturatedalkyl group which may have a substituent and an unsaturated alkyl groupwhich may have a substituent. The saturated alkyl groups include, forexample, a methyl, ethyl, butyl, octyl, dodecyl, tetradecyl, hexadecylor like group. The unsaturated alkyl groups include, for example, anethenyl, propenyl or like group.

The cycloalkyl groups represented by R¹ include, for example, such a 5-to 7-membered cycloalkyl group which may have a substituent as acyclopentyl, cyclohexyl or like group.

The aryl groups represented by R¹ include, for example, a phenyl ornaphthyl group which may have a substituent.

The substituents of the aliphatic, cycloalkyl and aryl groups eachrepresented by R¹ include, for example, an alkyl, aryl, alkoxy,carbonyl, carbamoyl, acylamino, sulfamoyl, sulfonamido, carbonyloxy,alkylsulfonyl, hydroxy, heterocyclic, alkylthio and arylthio groups andthe like; and these substituents each may have a further substituent.

In the above-given Formula [K], Y represents a simple link or divalenthydrocarbon group which is necessary to form a 5- to 7-memberedheterocyclic ring together with nitrogen, however, when Y is a simplelink, R⁵ and R⁷ may couple to each other to form a simple link so thatan unsaturated 5-membered heterocyclic ring may be formed and, when Y isa divalent hydrocarbon group, i.e., a methylene group, R⁵ and Y or R⁷and Y may form an unsaturated link so that an unsaturated 6-memberedheterocyclic ring may be formed, and further, when Y is an ethylenegroup, R⁵ and Y, R⁷ and Y or Y itself may form an unsaturated link sothat an unsaturated 7-membered heterocyclic ring may be formed. Inaddition to the above, the divalent hydrocarbon groups represented by Ymay have substituents, respectively. Such substituents include, forexample, an alkyl, carbamoyl, alkyloxycarbonyl, acylamino, sulfonamido,sulfamoyl, aryl, heterocyclic and like groups.

In the above-given Formula [K], R² R³, R⁴, R⁵, R⁶ and R⁷ representhydrogen, an aliphatic, cycloalkyl or aryl group. The aliphatic groupsrepresented by R² through R⁷ include, for example, a saturated alkylgroup which may have a substituent and an unsaturated alkyl group whichmay have a substituent. The saturated alkyl groups include, for example,a methyl, ethyl, butyl, octyl, dodecyl, tetradecyl, hexadecyl and likegroups; and the unsaturated alkyl groups include, for example, anethenyl, propenyl and like groups.

The cycloalkyl groups represented by R² through R⁷ include, for example,such a 5- to 7-membered cycloalkyl group which may have a substituent asa cyclopentyl, cyclohexyl or like group.

The aryl groups represented by R² through R⁷ include, for example, aphenyl, naphthyl or like group which may have a substituet.

The substituents of the aliphatic, cycloalkyl and aryl groupsrepresented by the above-denoted R² through R⁷ include, for example, analkyl, aryl, alkoxy, carbonyl, carbamoyl, acylamino, sulfamoyl,sulfonamido, cabonyloxy, alkylsulfonyl, arylsulfonyl, hydroxy,heterocyclic, alkylthio and like groups.

Among the compounds represented by the aforegiven Formula [K], thoseeach having a 5- to 7-membered saturated heterocyclic ring are morepreferable than those each having an unsaturated ring.

A mount of the compounds represented by the aforegiven Formula [K] to beused to preferably from 5 to 300 mol % and more preferably from 10 to200 mol %, to the magenta couplers of the invention represented by theaforegiven Formula [I].

The typical examples of the compounds represented by the aforegivenFormula [K] will be give below:

    __________________________________________________________________________     ##STR203##                                                                      R.sup.1                             R.sup.2                                                                          R.sup.3         R.sup.4                                                                         R.sup.5           __________________________________________________________________________    K-1                                                                              C.sub.8 H.sub.17                    H  H               H H                 K-2                                                                               ##STR204##                         H  H               H H                 K-3                                                                               ##STR205##                         H  H               H H                 K-4                                                                              C.sub.12 H.sub.25                   H  H               H H                 K-5                                                                              C.sub.14 H.sub.29                   H  H               H H                 K-6                                                                              C.sub.16 H.sub.33                   H  H               H H                 K-7                                                                              C.sub.14 H.sub.29                   H                                                                                 ##STR206##     H H                 K-8                                                                               ##STR207##                         CH.sub.3                                                                         CH.sub.3        H H                 K-9                                                                              C.sub.6 H.sub.5 CHCHCH.sub.2        H  H               H H                 K-10                                                                              ##STR208##                         H  H               H H                 __________________________________________________________________________     ##STR209##                                                                      R.sup.1      R.sup.2      R.sup.3 R.sup.4        R.sup.5                                                                          R.sup.6                __________________________________________________________________________    K-11                                                                             (t)C.sub.8 H.sub.17                                                                        H            H       H              H  H                      K-12                                                                              ##STR210##  H            H       H              H  H                      K-13                                                                             C.sub.12 H.sub.25                                                                          H            H       H              H  H                      K-14                                                                             C.sub.14 H.sub.29                                                                          H            H       H              H  H                      K-15                                                                             C.sub.16 H.sub.33                                                                          H            H       H              H  H                      K-16                                                                             C.sub.14 H.sub.29                                                                          CH.sub.3     H       H              H  H                      K-17                                                                              ##STR211##                       H              H  H                      K-18                                                                             C.sub.8 H.sub.17                                                                           CH.sub.3     CH.sub.3                                                                              H              CH.sub.3                                                                         CH.sub.3               K-19                                                                              ##STR212##  CH.sub.3     H       H              CH.sub.3                                                                         H                      K-20                                                                             CH.sub.3     H            H       C.sub.12 H.sub.25 OCOCH.sub.2                                                                H  H                      K-21                                                                             CH.sub.3     CH.sub.3     H       C.sub.16 H.sub.33 OCOCH.sub.2                                                                H  CH.sub.3               K-22                                                                             CH.sub.3     C.sub.16 H.sub.33                                                                          H       H              H  H                      K-23                                                                             C.sub.6 H.sub.5                                                                            H            H       C.sub.12 H.sub.25 OCO                                                                        H  H                      K-24                                                                             CH.sub.3     C.sub.6 H.sub.5                                                                            H       H              H  H                      K-25                                                                              ##STR213##  H            H       H              H  H                      __________________________________________________________________________     ##STR214##                                                                      R.sup.1                     R.sup.2                                        __________________________________________________________________________    K-26                                                                             C.sub.8 H.sub.17            H                                              K-27                                                                              ##STR215##                 H                                              K-28                                                                              ##STR216##                 H                                              K-29                                                                             C.sub.14 H.sub.29           H                                              K-30                                                                              ##STR217##                 H                                              K-31                                                                             C.sub.16 H.sub.33           CH.sub.3                                       K-32                                                                              ##STR218##                 H                                              K-33                                                                              ##STR219##                 H                                              K-34                                                                              ##STR220##                                                                K-35                                                                              ##STR221##                                                                K-36                                                                              ##STR222##                                                                K-37                                                                              ##STR223##                                                                K-38                                                                              ##STR224##                                                                K-39                                                                              ##STR225##                                                                K-40                                                                              ##STR226##                                                                K-41                                                                              ##STR227##                                                                __________________________________________________________________________

Next, the typical synthesis examples of the compounds represented by theFormula [K] will be given below:

SYNTHESIS EXAMPLE-1 (SYNTHESIS OF COMPOUND K-14)

Nine (9) grams of piperazine and 28 g of myristyl bromide were dissolvedin 60 ml of acetone and 6.0 g of anhydrous potassium carbonate were thenadded thereto. The resulted matter was boiled and refluxed for 20 hoursso as to undergo a reaction. After the reaction, the resulted reactantsolution was poured into 300 ml of water and an extraction was thentried with 300 ml of ethyl acetate. After the resulted ethyl acetatelayer was dried with magnesium sulfate, the ethyl acetate was distilledoff. Then, the white crystallized objective matter was obtained. Therecrystallization thereof was made with 100 ml of acetone and, then, 12g of white flaky crystals were obtained (yield: 43%).

Melting point: 175° to 180° C.

The hydrophilic colloidal layers such as a protective layer, aninterlayer and the like of the color photographic light-sensitivematerials for printing use of the invention are allowed to contain anultraviolet absorving agent with the purposes of preventing a fog causedby a static discharge generated by rubbing the light-sensitive materialsand avoiding the deterioration of an image caused by exposing thelight-sensitive materials to ultraviolet rays.

To the color photographic light-sensitive materials for printing use ofthe invention, there may be provided with the supplementary layers suchas a filter layer, an antihalation layer and/or an antiiradiation layer.These layers and/or emulsion layers may also contain such a dyestuff asis capable of flowing out from the light-sensitive materials or beingbleached, in a developing process.

To the silver halide emulsion layers and/or the other hydrophiliccolloidal layers of the color photographic light-sensitive matrials forprinting use of the invention, there may be added with a matting agentwith the purpose of reducing the gross of the light-sensitive materialsand improving the retouchability and further avoiding the adhesion ofthe light-sensitive materials to each other.

To the color photographic light-sensitive matrials for printing use ofthe invention, there may be added with a sliding agent with the purposeof reducing a sliding friction.

To the color photographic light-sensitive matrials for printing use ofthe invention, there may be added with an antistatic agent with thepurpose of preventing a static charge. Such an antistatic agent issometimes provided to an antistatic layer arranged to the side of thesupport of the light-sensitive material whereon no emulsion is coated,or the antistatic agent may also be provided, in other cases, to aprotective layer other than the emulsion layers, which is arranged tothe side of the emulsion layer and/or the support whereon the emulsionis coated.

To the photographic emulsion layers and/or the other hydrophiliccolloidal layers of the color photographic light-sensitive materials forprinting use of the invention, various surface active agents maybeapplied with the purposes of improving the coating behavior, preventingthe static charge, improving the slidability, improving theemulsification=dispersion property, preventing the adhesion, improvingthe photographic characteristics such as a development acceleration,hardening, sensitization, and the like.

For the purpose of color-reproducing an image in a color substractionprocess, the reflection type support of a color photographiclight-sensitive material for color printing use of the invention isprovided thereon with silver halide emulsion layers andnon-light-sensitive layers, in suitable quantity and arrangement order,containing a magenta, yellow and cyan couplers each serving as thecouplers for photographic use. Such quantity and arrangement order tothe layers may suitably be changed according to the priority propertiesand the purposes of using.

The color photographic light-sensitive materials for printing use of theinvention may be coated to the surface of the support thereof directlyor with the interposition of one or not less than two subbing layersbetween them for improving the surface of the support on its adhesionproperty, antistatic property, dimensional stability, abrasionresistance, hardness, antihalation property, friction property and/orother properties, after applying a corona discharge, an ultraviolet rayirradiation, a flame treatment or the like to the surface of thesupport, if required.

In coating the color photographic light-sensitive materials for printinguse of the invention, a thickening agent may be used to improve thecoatability. An extrusion coating method and a curtain coating methodare particularly useful for this purpose, because two or more layers maybe coated at the same time in these methods.

In the color photographic light-sensitive materials for printing use ofthe invention, images may be reproduced in any color developmentswell-known to the skilled in the art.

In the invention, the aromatic primary amine color developing agents tobe used in a color developer include any well-known ones being popularlyused in various color photographic processes. These developers include,for example, an aminophenol derivative and a p-phenylenediaminederivative. These compounds are generally used in the form of the saltsthereof, such as a chloride or sulfate, rather than in the free state,because the salts are more stable. Such compounds are generally used ata cendensation of from about 0.1 g to about 30 g per liter of a colordeveloper used and more preferably from about 1 g to about 15 g perliter of the color developer used.

Such aminophenol developers include, for example, o-aminophenol,p-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene,2-oxy-3-amino-1,4-dimethylbenzene, and the like.

The particularly useful aromatic primary amine color developers include,for example, a N,N'-dialkyl-p-phenylene diamine compound, and the alkyland phenyl groups thereof may be substituted by any arbitrarysubstituents. Among the compounds, the particularly useful compoundsinclude, for example, a N,N'-diethyl-p-phenylenediamine chloride, aN-methyl-p-phenylenediamine chloride, a N,N'-dimethyl-p-phenylenediaminechloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, aN-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate,N-ethyl-N-β-hydroxyethylaminoaniline,4-amino-3-methyl-N,N'-diethylaniline,4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluene sulfonate,and the like.

In the processes of the invention, the color developers used contain theabove-mentioned aromatic primary amine color developing chemicals and inaddition they are further allowed to contain nay various componentswhich are normally added to color developers, including, for example,such an alkalizer as sodium hydroxide, sodium carbonate, potassiumcarbonate; an alkali metal sulfite, an alkali metal bisulfite, an alkalimetal thio- cyanate, an alkali metal halide, benzyl alcohol, a watersoftening agent, a thickening agent and the like. A pH value of theabove-mentioned color developers is normally not lower than 7 and mostpopularly from about 10 to about 13.

In the invention, a color photographic light-sensitive material forprinting use is color-developed and is then processed with a processingliquid capable of fixing the light-sensitive material. When theprocessing liquid capable of fixing is a fixer, a bleaching step is tobe taken before the fixing step. As for the bleaching agents to be usedin such a bleaching step, the metallic complex salts of an organic acidare used. Such metallic complex salts have the function that a metallicsilver produced by a development is oxidized and restored to the silverhalide thereof and, at the same time, the undeveloped color portions ofa color-developing chemical are color-developed. Such a metal complexsalts is composed of an aminopolycarboxylic acid or such an organic acidas oxalic acid, citric acid or the like, with which such a metal ions asthat of iron, cobalt, copper or the like are coordinated. The organicacids most preferably useful to form such a metal complex salt thereofas mentioned above include, for example, a polycarboxylic acid oraminocarboxylic acid. These polycarboxylic acid or aminocarboxylic acidmay alternatively be an alkali metallic salt, an ammonium salt or awater-soluble amine salt.

The typical examples thereof may be given below:

[1] Ethylenediaminetetraacetic acid,

[2] Nitrilotriacetic acid

[3] Iminodiacetic acid,

[4] Disodium ethylenediaminetetraacetate,

[5] Tetra(Tri)methylammonium ethylenediaminetetraacetate

[6] Tetrasodium ethylenediaminetetraacetate, and

[7] Sodium nitrilotriacetate.

The bleaching agents to be used therein contain various additives aswell as the above-mentioned metallic complex salts of the organic acidsto serve as the bleaching agents. It is desirable that such an additivecontains an alkali halide or ammonium halide in particular including,for example, a rehalogenater such as potassium bromide, sodium bromide,sodium chloride, ammonium bromide or the like, a metallic salt and achelating agent.

It is also allowed to suitably add such a matter as a borate, oxalate,acetate, carbonate, phosphate or like salts which is well-known to beput into a pH buffer, and such a metter as an alkylamine, polyethyleneoxide or the like which is well-known to be put into an ordinary typebleaching liquid.

In addition to the above, the fixers and the bleach-fixers are alsoallowed to contain a single or not less than two kinds of pH bufferscomprising such a sulfite as ammonium sulfite, potassium sulfite,ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammoniummetabisulfite, potassium metabisulfite, sodium metabisulfite and thelike, and various kinds of salts such as a boric acid, borax, sodiumhydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,sodium bisulfite, sodium bicarbonate, potassium bicarbonate, aceticacid, sodium acetate, ammonium hydroxide and the like.

When a process of the invention is carried out while adding a bleach-fixreplenisher to a bleach-fix solution (bath), the bleach-fix solution(bath) may contain a thiosulfate, a thiocyanate, a sulfite or the like,or the bleach-fix replenisher may contain the above-mentioned salts tobe replenished to a processing bath.

In the invention, for a further activation of a bleach-fixer, the air oroxygen may be blown, if desired, through the bleach-fixing bath and thereservoir of a bleach-fix replenisher, or such a suitable oxidizer ashydrogen peroxide, a bromate, a persulfate and the like may suitably beadded thereto.

EXAMPLES

Now, the invention will be descrived in detail with reference to thefollowing embodiments, and it is, however, to be understood that theinvention shall not be limited thereto.

EXAMPLE-1

In the presence of an inert gelatin, there prepared, in a normal (orsingle-jet) prepcipitation process, a polydispersed silver chlorobromideemulsion (whose silver bromide content: 80 mol %) having the averagegrain size (r) of 0.60 μm and the variation coefficient (s/r) of 0.25;and the resulted emulsion was further added with sodium thiosulfate andthe following spectral sensitizing dye (D-1) at 50° C., so that theEmulsion EM-1 was obtained.

Next, the emulsion EM-1 prepared as above for serving as a greensensitive emulsion, the following coupler (M-1) for serving as a magentacoupler and the aforementioned high boiling organic solvent (S-3) weredispersed in an aqueous gelatin solution by making use of a supersonicdispersing device, and the resulted dispersed solution was coated toform the third layer on a paper support coated with polyethylene on theboth sides thereof, and the other layers each comprising thecompositions shown in Table were coated respectively on the papersupport, so that a multilayered color photographic light-sensitivematerial for printing use were prepared and named Sample-1.

                  TABLE-1                                                         ______________________________________                                        7th layer Gelatin                                                                       Hardener (H-1)                                                      6th layer Ultraviolet absorber (UV-1)                                                   Gelatin                                                             5th layer Red-sensitive silver chlorobromide emulsion                                   (Silver bromide content: 60 mol %;                                            Silver coated: 0.25 g/m.sup.2)                                                Cyan coupler (C-1)                                                            Dioctyl phthalate                                                             Gelatin                                                             4th layer Ultraviolet absorbing agent (UV-1)                                  3rd layer Green sensitive emulsion (EM-1)                                               (Silver coated: 0.40 g/m.sup.2)                                               Magenta coupler                                                               Dioctyl phthalate                                                             Gelatin                                                             2nd layer Gelatin                                                             1st layer Blue sensitive silver chlorobromide emulsion                                  (Silver bromide content: 90 mol %;                                            Silver coated: 0.35 g/m.sup.2)                                                Yellow coupler (Y-1)                                                          Dioctyl phthalate                                                             Gelatin                                                             Support                                                                       ______________________________________                                    

Next, in the presence of an insert gelatin, there prepared, in adouble-jet precipitation process, a monodispersed silver chlorobromideemulsion (whose silver bromide content: 80 mol %) having the averagegrain size (r) of 0.53 μm and the variation coefficient (s/r) of 0.13with regulating the flow at 50° C. to meet the conditions for notproducing any new grains in the course of grain growth. The resultedemulsion was added with sodium thiosulfate and the following spectralsensitizing dye D-1 at 55° C., so that the emulsion EM-2 was obtained.

Now, Samples 2 and 3 were prepared respectively in the same manner as inSample-1 except that the emulsion EM-2 prepared as described above wereused in the both samples and the silver coated weight of the greensensitive emulsion were 0.35 g/m² and 0.32 g/m², respectively.

Then, a monodispersed chlorobromide emulsion (Silver bromide content: 80mol %) having the average grain size (r) of 0.39 μm and the variationcoefficient (s/r) of 0.14 was prepared in the same manner as in thepreparation of the emulsion EM-2 except that the mixing temperature wasset at 40° C., and the resulted emulsion was chemically sensitized inthe same manner as in the emulsion EM-2, so that the emulsion EM-3 wasobtained.

Further, a monodispersed silver chlorobromide emulsion having theaverage grain size (r) of 0.65 μm and the variation coefficient (s/r) of0.12 in the same manner as taken in the case of the emulsion EM-2 exceptthat the mixing temperature was changed to 60° C., and the resultedemulsion was chemically sensitized as was treated in the case of theemulsion EM-2, so that the emulsion EM-4 was obtained.

Still further, Samples 4 and 5 were prepared in the same manner as inthe case of the emulsion EM-1, except that the emulsions EM-3 and 4 weremixed up in the proportion of the silver contents between them wereadjusted to 1:1 and the mixture was coated to serve as a green sensitiveemulsion in the amounts of silver coated of 0.37 g/m² and 0.34 g/m²,respectively.

Next, Sample-6 was prepared in the same manner as in Sample-1, exceptthat the Exemplified Magenta Coupler (44) was used and the greensensitive emulsion was coated in an amount of 0.20 g/m² in the terms ofsilver content.

Further, Sample-7 was prepared in the same manner as in Sample-2, exceptthat the Exemplified Magenta Coupler (44) was used and the greensensitive emulsion was coated in an amount of 0.17 g/m² in the terms ofsilver content.

Still further, Sample-8 was prepared in the same manner as in Sample-4,except that the Exemplified Magenta Coupler (44) was used and the greensensitive emulsion was coated in an amount of 0.19 g/m² in the terms ofsilver content.

Now, the respective structures of the yellow coupler (Y-1), the magentacoupler (M-1), the cyan coupler (C-1), the ultraviolet absorber (UV-1),the hardener (H-1) and the spectral sensitizing dye (D-1) which wereused in Samples 1 through 8 will be given below: ##STR228##

With respect to the resulted Samples 1 through 8, the gradationcharacteristics thereof (in particular, the attention was paid to thecolor-balance of each sample) were evaluated in the following manner:

How to evaluate the gradation characteristics (Color balance)

The above-mentioned Samples 1 through 8 were exposed to light by makinguse of a sensitometer (Model KS-7 manufactured by Konishiroku PhotoIndustry Co., Ltyd., Japan) through an optical wedge, and were thenprocessed according to the following processing steps, respectively,provided that each of the exposure was so conditioned as to adjust thecolor density obtained after processed to the neutral, at a density ofabout 1.0.

    ______________________________________                                        [Developing Process]                                                          ______________________________________                                        Color developing step:                                                                        38° C.                                                                           3 min. 30 sec.                                      Bleach-fixing step:                                                                           33° C.                                                                           1 min. 30 sec.                                      Washing step:   25˜35° C.                                                                  3 min.                                              Drying step:    77˜80° C.                                                                  About 2 min.                                        ______________________________________                                    

    ______________________________________                                        [Color developer]                                                             Benzyl alcohol            15     ml.                                          Ethylene glycol           15     ml.                                          Potassium sulfite         2.0    g.                                           Potassium bromide         0.7    g.                                           Sodium chloride           0.2    g.                                           Potassium carbonate       30.0   g.                                           Hydroxylamine sulfate     3.0    g.                                           Polyphosphoric acid (TPPS)                                                                              2.5    g.                                           3-methyl-4-amino-N-ethyl-N-(β-methane                                                              5.5    g.                                           sulfonamidoethyl)-aniline sulfonate                                           Brightening agent (a 4,4'-diamino                                                                       1.0    g.                                           stilbenedisulfonic acid derivative)                                           potassium hydroxide       2.0    g.                                           Add water to make a total amount to                                                                     1      liter                                        Adjust the pH value to    10.20                                               [Bleach-fixer]                                                                Ferric ammonium ethylenediamine                                                                         60.0   g.                                           tetraacetate dihydrate                                                        Ethylenediaminetetracetic acid                                                                          3.0    g.                                           Ammonium thiosulfate (a 70% solution)                                                                   100    ml.                                          Ammonium sulfite (a 40% solution)                                                                       27.5   ml.                                          Adjust the pH value with potassium carbonate                                                            7.1                                                 or glacial acetic acid to                                                     Add water to make a total amount to                                                                     1      liter.                                       ______________________________________                                    

The processed samples resulted thereby were evaluated for the neutralityat the density points of about 0.5, 1.0, 1.5 and 2.0, by making use of astandard color chip (provided according to JIS Z8721 supervided by TheJIS Color Chip Committe of The Japan Standards Association). In theevaluation of such gradation characteristics, a sample having theneutrality in every density area is to be graded as the best and asample having the more shifted density is graded as the worse ingradation characteristics.

The results therefrom are shown in Table 2, below.

Wherein, with respect to the evaluation of the neutrality in the densitypoints of about 0.5, 1.0, 1.5 and 2.0, N indicates that an approximateneutrality is reproduced, and M, C, B and G indicate a shift from theneutrality to magenta, cyan, blue and green, respectively.

                                      TABLE 2                                     __________________________________________________________________________                                      Evaluation of neutrality                                              Silver amount                                                                         Density                                                                            Density                                                                            Density                                                                            Density                                        Green sensitive                                                                       coated to 3rd                                                                         at abt.                                                                            at abt.                                                                            at abt.                                                                            at abt.                      Sample No.                                                                             Magenta coupler                                                                        emulsion                                                                              layer (g/m.sup.2)                                                                     0.5  1.0  1.5  2.0                          __________________________________________________________________________    1 (Comparative)                                                                        M-1      EM-1    0.40    N    N    N    N                            2 (Comparative)                                                                        "        EM-2    0.35    C˜B                                                                          N    M    M                            3 (Comparative)                                                                        "        "       0.32    C˜B                                                                          N    N    G                            4 (Comparative)                                                                        "        EM-3 + EM-4                                                                           0.37    N    N    N    M                            5 (Comparative)                                                                        "        "       0.34    N    N    G    N                            6 (Comparative)                                                                        Exemplified                                                                            EM-1    0.20    M    N    N    G                                     compound 44                                                          7 (Invention)                                                                          Exemplified                                                                            EM-2    0.17    N    N    N    N                                     compound 44                                                          8 (Invention)                                                                          Exemplified                                                                            EM-3 + EM-4                                                                           0.19    N    N    N    N                                     compound 44                                                          __________________________________________________________________________

As is obvious from the results shown in Table 2, it can be understoodthat the samples each combined the monodispersed emulsion of theinvention with the magenta coupler of the invention (i.e., Samples 7 and8) are excellent in gradation characteristics.

Next, with the purpose of checking up other photographic characteristicsthan the gradation characteristics, the samples 1 through 8 wereevaluated for sensitivity to pressure-induced desensitization in themethod described below. The results therefrom are shown in Table 3.

Evaluation of Sensitivity to Pressure-induced Desensitization

A sample is so uniformly exposed to light as to make the magent colordensity after the development be about 0.5 ans is bent along a piece ofstainless-steel rod of 5 mm in diameter at 25° C. and 25% RH. Theresulting sample is color-developed in the same manner as in the casesof examples memtioned above and is then measured of the magent density.In this case, the less the variation of the density is, the less thesensitivity to pressure-induced desensitization is.

                  TABLE 3                                                         ______________________________________                                        Sample No.      Sensitivity to pressure                                       ______________________________________                                        1 (For comparison)                                                                            -0.15                                                         2 (For comparison)                                                                            -0.01                                                         3 (For comparison)                                                                             0.00                                                         4 (For comparison)                                                                            -0.02                                                         5 (For comparison)                                                                            -0.02                                                         6 (For comparison)                                                                            -0.13                                                         7 (of Invention)                                                                              -0.01                                                         8 (of Invention)                                                                              -0.01                                                         ______________________________________                                    

It is found from the Table 3 that, with respect to the sensitivity topressure-induced desensitization, the Samples 1 and 6 were considerablylowered in density and were at the level practically causing rubs, whilethe other samples were at the level practically causing no rub at all.

It is also found from the results mentioned above that Sample 1 was atthe level causing no rub in gradation characteristics, however, thissample has the serious defects in manufacturing costs because itrequires a large amount of silver to be coated, and in the photographicproperties, so that this sample cannot satisfy the objets of theinvention.

In the Samples 2, 3, 4 and 5, it is found that the gradationcharacteristics are not fully satisfied by only making use of themagenta coupler of the invention, but the invention using themonodispersed emulsion of the invention and the magenta coupler of theinvention is combination is the only way for obtaining a colorphotographic light-sensitive material for printing use which isexcellent in gradation characteristics and sensitivity topressure-induced desensitization and is also capable of beingmanufactured at an inexpensive cost.

EXAMPLE-2

Samples 9 through 21 were prepared in the same manner as taken in thecase of Example-1 except that the emulsions, EM-1 and EM-2, were used toserve as the green-sensitive emulsion, and the magenta coupler and thecoating weight of silver were conditioned as shown in Table 4 and,further, the solvent, S-12, were used to serve as the high-boilingorganic solvent for the magenta coupler.

With respect to the above-mentioned Samples 9 through 21, the gradationcharacteristics thereof were evaluated in the same manner as inExample-1, respectively. The results therefrom are shown in Table 4,below.

The sensitivity to pressure-induced desensitization thereof were alsoevaluated in the same manner as in Example-1, and the results therefromare shown in Table 4, together.

For reference, the structures of the magenta couplers, M-2 and M-3,indicated in Table 4 are given below: ##STR229##

                                      TABLE 4                                     __________________________________________________________________________                                      Evaluation of neutrality                                      Green   Coating wt. of                                                                        Density                                                                            Density                                                                            Density                                                                            Density                                                                            Sensitivity to                            sensitive                                                                             silver to 3rd                                                                         at abt.                                                                            at abt.                                                                            at abt.                                                                            at abt.                                                                            pressure-induced        Sample No.                                                                             Magenta coupler                                                                        material                                                                              layer (g/m.sup.2)                                                                     0.5  1.0  1.5  2.0  desensitization         __________________________________________________________________________     9 (Invention)                                                                         Exemplified                                                                            EM-2    0.16    N˜G                                                                          N    N    N    -0.03                            compound 5                                                           10 (Invention)                                                                         Exemplified                                                                            "       0.17    N˜G                                                                          N    N    N    -0.02                            compound 18                                                          11 (Invention)                                                                         Exemplified                                                                            "       0.17    N    N    N    N    -0.01                            compound 28                                                          12 (Invention)                                                                         Exemplified                                                                            "       0.18    N    N    N    N    -0.01                            compound 45                                                          13 (Invention)                                                                         Exemplified                                                                            "       0.16    N    N    N    N    -0.02                            compound 59                                                          14 (Invention)                                                                         Exemplified                                                                            "       0.19    N˜M                                                                          N    N    N    -0.03                            compound 104                                                         15 (Invention)                                                                         Exemplified                                                                            "       0.17    N    N    N    N    -0.03                            compound 127                                                         16 (Invention)                                                                         Exemplified                                                                            "       0.19    N    N    N    N    -0.04                            compound 152                                                         17 (Comparative)                                                                       M-2      EM-2    0.18    G    N    M    M    -0.01                   18 (Comparative)                                                                       "        "       0.16    C˜G                                                                          N    N    G    -0.02                   19 (Comparative)                                                                       "        EM-1    0.19    N    N    N    N    -0.17                   20 (Comparative)                                                                       M-3      EM-2    0.35    M    N    G    G     0.00                   21 (Comparative)                                                                       "        "       0.38    M    N    N    M    -0.01                   __________________________________________________________________________

It is found from the results shown in Table 4 that a color photographiclight-sensitive material for printing use which is excellent ingradation characteristics and other photographic properties and is alsocapable of being manufactured at an inexpensice cost that is the objectof the invention can be prepared solely by the constitution of theinvention comprising a green-sensitive emulsion containing thecombination of a monodispersed emulsion and the magenta coupler of theinvention having a specific structure.

What is claimed is:
 1. A color photographic light-sensitive materialwhich comprises a reflective support and a blue sensitive silver halideemulsion layer, a green sensitive silver halide emulsion layer, and ared sensitive silver halide emulsion layer, said green sensitive silverhalide emulsion layer comprising a magenta coupler and a monodispersedsilver chlorobromide emulsion; wherein said monodispersed silverchlorobromide emulsion has an S/r ratio of not more than 0.22, wherein Sis a statistical standard deviation of grain size and r is an averagegrain size,said magenta coupler being represented by Formula II or III##STR230## wherein the R's, which may be the same or different,represent hydrogen or a substituent, and X represents a substituentcapable of splitting off through a reaction thereof with oxidationproducts of a color developing agent.
 2. The material of claim 1 whereinr is 0.25 to 0.75 μm.
 3. The material of claim 2 wherein r is 0.35 to0.65 μm.
 4. The material of claim 1 wherein said silver chlorobromideemulsion contains silver chlorobromide grains having at least 5 mol % ofsilver chloride.
 5. The material of claim 4 wherein said silverchlorobromide emulsion contains silver chlorobromide grains with asilver chloride content of at least 15 mol %.